ACID, SOLVENT, AND THERMAL RESISTANT METAL-ORGANIC FRAMEWORKS

Abstract

The disclosure provides for thermal, solvent, and/or acid resistant metal organic frameworks and the use of these frameworks in devices and methods for gas separation, gas storage, and catalysis. The disclosure further provides for MOFs that are strong solid acids, and the use of these strong solid acid MOFs in catalytic devices and catalytic methods.

Description

TECHNICAL FIELD

This disclosure provides for acid, solvent, and/or thermal resistant Metal-Organic Frameworks (MOFs), including solid-acid MOFs (sa-MOFs), and the use of the MOFs for gas adsorption, gas separation, and catalysis.

BACKGROUND

Metal-organic frameworks (MOFs) are porous crystalline materials that are constructed by linking metal clusters called Secondary Binding Units (SBUs) and organic linking moieties. MOFs have high surface area and high porosity which enable them to be utilized in diverse fields, such as gas storage, catalysis, and sensors.

SUMMARY

The disclosure provides for metal-organic frameworks (MOFs) that are acid, solvent, and/or thermal resistant. The MOFs of the disclosure can be used in a variety of applications and environments that cannot be addressed by using conventional framework materials. The MOFs of the disclosure comprise metals (e.g., titanium, zirconium, and hafnium) coordinated to carboxylate clusters of organic linking ligands. The disclosure further provides for controlling metal-carboxylate cluster extensions and topologies of the MOFs by using the methods disclosed herein. The MOFs of the disclosure are comprised of organic linking moieties having various geometries, multivariate functionalities and metalation. Further, isomorphous analogues of the MOFs disclosed herein can be created by replacing framework metal ions with alternate metal ions. Accordingly, the disclosure provides for a new series of MOFs that feature: acid, solvent, and/or thermal resistance; designable topologies; multivariate framework components; controllable pore metrics; and tunable pore environments. The disclosure further provides for MOFs comprised of Zr-carboxylate SBUs linked to various organic linking ligands (e.g., MOF-801, MOF-802, MOF-803, MOF-804, MOF-805, MOF-806, MOF-807, MOF-808, MOF-812, MOF-841, and MOF-841).

The disclosure also provides for a framework comprising zirconium and benzene-tribenzoic acid (BTB)-based organic linking moieties (e.g., MOF-777). MOF-777 is thermally stable up to 550° C., and is resistant to common acids, bases, organic solvents and water. MOF-777 has a unique tfz-d type 3D topology that is based on stacking kgd-a type 2D structures which is built around hexagonal SBUs and triangle BTB-based linkers. The topology of MOF-777 is unique and the first of its kind in the field. Therefore, MOF-777 represents an entirely new class of MOFs which substructure allows for exfoliation. The disclosure additionally provides for variations of the MOF-777 framework which comprise substituting zirconium metal ions with alternate metal ions, substituting the BTB organic linking ligand with alternate organic linking ligands which have trigonal planar geometries, and/or substituting formate anions with alternate linking anions.

As the MOFs of the disclosure are typically acid resistant they can be also be modified to be strong solid-acids, by (1) modifying linking anions used to synthesize the frameworks with acidic site precursors capable of becoming Bronstead and/or Lewis acids (e.g., sulfate, and halide anions); (2) complexing open metal sites or other portions (e.g., pore) of the MOFs disclosed herein with acidic site precursors; and (3) exchanging anions coordinated to the metal, metal ions, or metal containing complexes of the MOFs with acidic site precursors. Further, due to the highly adsorptive nature of the MOFs disclosed herein, MOFs that are strong solid-acids are capable of being superacids.

The disclosure further provides that the MOFs disclosed herein can be used in variety of applications and devices, including, for use in fluid storage, fluid separation, thin films, catalysis, sensors, adsorbents (e.g., radioactive isotopes, and for harmful chemicals), conductors, and in the manufacture fertilizers, batteries, dyes, paints, drugs and explosives.

The disclosure provides a thermal, acid, and/or solvent resistant metal organic framework (MOF) comprising a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is an organic linking ligand comprising one or more structures of Formula I-XII:

wherein, A¹-A⁸ are independently a C, N, O, or S; A⁹ is selected from

X¹-X⁸ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and R¹-R¹⁸⁶ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and wherein the framework is thermally stable when exposed to a temperature between 50° C. to 525° C., and/or the framework is chemically stable in the presence of a solvent and/or an acid. In another embodiment, L is a linear diptopic organic linking ligand comprising one or more structures of Formula V-VII:

wherein, R³⁷-R⁵⁴ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system. In yet another embodiment, L is a linear diptopic organic linking ligand comprising one or more structures of Formula V(a), VI(a), VI(b) and VII(a):

In another embodiment, L is a bent diptopic organic linking ligand comprising one or more structures of Formula VIII-XV:

wherein, A⁴-A⁸ are independently a C, N, O, or S; A⁹ is selected from

X⁴-X⁸ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and R⁵⁵-R¹⁰² are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system. In yet a further embodiment, L is a bent diptopic organic linking ligand comprising one or more structures of Formula VIII(a), VIII(b), VIII(c), VIII(d), VIII(e), VIII(f), VIII(g), VIII(h), IX(a), X(a), XI(a), XII(a), XIII(a), XIV(a), XV(a), XV(b), and XV(c):

In another embodiment, L is a tetratopic organic linking ligand comprising one or more structures of Formula XVI-XXII:

wherein, R²⁵-R³⁶, R⁵⁵-R⁵⁸, R⁶⁰, R⁶¹, R⁶³, R⁶⁴, R¹⁰³-R¹⁸⁶ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system. In an further embodiment, L is a tetratopic organic linking ligand comprising one or more structures of Formula XVI(a), XVII(a), XVIII(a), XIX(a), XX(a), XXI(a) and XXII(a):

In another embodiment, L is a tritopic organic linking ligand having one or more structures of Formula I-IV:

wherein, A¹-A³ are independently a C, N, O, or S; X¹-X³ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and R¹-R³⁶ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system. In another embodiment, L is a tritopic organic linking ligand comprising one or more structures of any one of Formula I-IV:

wherein, A¹-A³ are independently a C, N, O, or S; X¹-X³ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and R¹, R³-R⁵, R⁷-R⁹, R¹¹-R¹³, R¹⁵-R¹⁷, R¹⁹-R²¹, R²³-R²⁵, R²⁷-R²⁹, R³¹-R³³, R³⁵- R³⁶ are H; and R², R⁶, R¹⁰, R¹⁴, R¹⁸, R²², R²⁶, R³⁰ and R³⁴ are independently selected from amino, methyl, hydroxyl, ═O, ═S, halo, optionally substituted aryl, optionally substituted aryloxy, alkoxy, —O—(CH₂)_n—CH₃, and —O—(CH₂)₂—O—CH₂—CH₃, wherein n is an integer from 2 to 5. In a further embodiment, L is a tritopic organic linking ligand comprising one or more structures of Formula I(a), II(a), III(a) and IV(a):

In another embodiment of any of the foregoing M is a metal or metal ion selected from Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁺, Hf³⁺, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²⁺, Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr, Mo⁶⁺, Mo⁵⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W²⁺, W⁺, W, Mn⁷⁺, Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺, Re²⁺, Re⁺, Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺, Os²⁺, Os⁺, Os, Co⁵⁺, Co⁴⁺, Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺, Ir⁴⁺, Ir³⁺, Ir²⁺, Ir⁺, Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺, Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag³⁺, Ag²⁺, Ag⁺, Au⁵⁺, Au⁴⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺, B²⁺, B⁺, Al³⁺, Al²⁺, Al⁺, Ga³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In¹⁺, Tl³⁺, Tl⁺, Si⁴⁺, Si³⁺, Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶⁺, Te⁵⁺, Te⁴⁺, Te²⁺, La³⁺, La²⁺, Ce⁴⁺, Ce³⁺, Ce²⁺, Pr⁴⁺, Pr³⁺, Pr²⁺, Nd³⁺, Nd²⁺, Sm³⁺, Sm²⁺, Eu³⁺, Eu², Gd³⁺, Gd²⁺, Gd⁺, Tb⁴⁺, Tb³⁺, Tb²⁺, Tb⁺, Db³⁺, Db²⁺, Ho³⁺, Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺, Yb³⁺, Yb²⁺, Lu³⁺, and combinations thereof, including any complexes which contain the metals or metal ions listed above, as well as any corresponding metal salt counter-anions. In a further embodiment, M is a metal or metal ion selected from Li⁺, Mg²⁺, Ca²⁺, Al³⁺, Al²⁺, Al⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁺, Hf³⁺, and combinations thereof, including any complexes which contain the metal ions listed, as well as any corresponding metal salt counter-anions. In yet another embodiment of any of the foregoing embodiments, the MOF is MOF-778 (hf-MOF-777). In a further embodiment, M is a zirconium metal or zirconium metal ion, including any complexes which contain zirconium, as well as any corresponding metal salt counter-anions. In another embodiment, the plurality of linked M-O-L SBUs are zirconium carboxylate clusters that have 3-c, 4-c, 6-c, 8-c, 9-c, 10-c, or 12-c extensions. In yet a further embodiment, the MOF is MOF-801, MOF-802, MOF-803, MOF-804, MOF-805, MOF-806, MOF-807, MOF-808, MOF-812, MOF-841, MOF-842 or MOF-867. In another embodiment, the plurality of linked M-O-L SBUs are hexagonal zirconium carboxylate clusters linked by benzene-tribenzoic acid (BTB)-based organic linking moieties. In a further embodiment, the MOF has tfz-d type 3D topology that is based upon the stacking of kgd-a type 2D layers. In yet a further embodiment, the layers are connected to each other via linking anions. In yet a further embodiment, the linking anions are selected from formate, acetate, phthalate, lactate, oxalate, citrate, fumurate, adipate, anthranilate, ascorbate, benzoate, butyrate, lactate, malate, malonate, tatrate, succinate, sorbate, cinnamate, glutamate, gluconate, propionate, pavalate, and valerate. In another embodiment, the linking anion is formate. In yet another embodiment, the MOF is MOF-777. In another embodiment, the linking anions comprise acid site precursors. In yet a further embodiment, the acid site precursors are selected from F⁻, Cl⁻, ClO⁻, ClO₂⁻, ClO₃⁻, ClO₄⁻, Br⁻, BrO⁻, I⁻, IO₃⁻, IO₄⁻, NO₃⁻, S₂⁻, HS⁻, HSO₃⁻, SO₃²⁻, SO₄²⁻, HSO₄⁻, H₂PO₄²⁻, PO₄³⁻, CO₃²⁻, HCO₃⁻, H₃BO₃, SiO₃²⁻, PF₆⁻, CF₃CO₂⁻ and CF₃SO₃⁻. In yet another embodiment, the acid site precursor is HSO₃⁻. In another embodiment, the MOF is a strong solid-acid (sa-MOF).

The disclosure also provides a method for producing a strong solid acid MOF (sa-MOF) comprising reacting the organic linking ligand as described above with a zirconium or hafnium metal or metal ion at an elevated temperature for at least 2 hours, in the presence of an acid site precursor. In one embodiment, the acid site precursor compound is selected from F⁻, Cl⁻, ClO⁻, ClO₂⁻, ClO₃⁻, ClO₄⁻, Br⁻, BrO⁻, I⁻, IO₃⁻, IO₄⁻, NO₃⁻, S₂⁻, HS⁻, HSO₃⁻, SO₃²⁻, SO₄²⁻, HSO₄⁻, H₂PO₄²⁻, PO₄³⁻, CO₃²⁻, HCO₃⁻, H₃BO₃⁻, SiO₃²⁻, PF₆⁻, CF₃CO₂⁻ and CF₃SO₃⁻. In another embodiment, the organic linking ligand comprises a structure of Formula I(a), II(a), III(a), or IV(a):

The disclosure also provides a sa-MOF produced by a method described above.

The disclosure also provides a gas storage and/or separation device comprising a MOF of the disclosure.

The disclosure also provides a device comprising a thin film or membrane of a MOF of the disclosure.

The disclosure also provides a catalytic device comprising a sa-MOF of the disclosure.

DESCRIPTION OF DRAWINGS

FIG. 1 provides examples of unsaturated zirconium-carboxylate SBUs with variable extension numbers, including a (12-c.) cuboctahedron SBU, a (10-c.) bicapped cube SBU, a (9-c.) tricapped trigonal-antiprism SBU, a (8-c.) cube SBU, a (6-c.) trigonal antiprism SBU, a (4-c.) square SBU, a (4-c.) Tetrahedron SBU, and a (3-c.) triangle SBU. Zr-carboxylate based SBUs have, at the least, the following advantages: high-symmetry, diverse geometries, robustness, and structural prediction.

FIG. 2A-F provides examples of Zr-MOFs by incorporating short/bent linkers with extensions of 12-c. Zr₆O₄(OH)₄(CO₂)₁₂ SBU, 10-c. Zr₆O₆(OH)₂(CO₂)₁₀ and 8-c. Zr₆O₈(CO₂)₈ SBUs. (A) Crystal structure of MOF-801 with octahedral cages (pore fixed size of 7.0 Å) and tetrahedral cages (pore fixed size of 5.4 Å); (B) Crystal structure of MOF-802 with octahedral cages (pore fixed size of 5.6 Å) and tetrahedral cages (pore fixed size of 4.0 Å); (C) Crystal structure of MOF-804 with truncated cubic cages (pore fixed size of 13.6 Å) and octahedral cages (pore fixed size of 8.8 Å); (D) Underlying topology of MOF-801 termed fcu-net; (E) Underlying topology of MOF-802 termed bet-net; and (F) Underlying topology of MOF-803 termed reo-net.

FIG. 3A-C provides examples of hydroxyl-functionalized MOFs by incorporating linear ditopic linkers with extended 12-c. Zr₆O₄(OH)₄(CO₂)₁₂ SBUs. (A) Crystal structure of MOF-804 with octahedral cages (pore fixed size of 6.8 Å) and tetrahedral cages (pore fixed size of 7.2 Å); (B) Crystal structure of MOF-805 with octahedral cages (pore fixed size of 8.8 Å) and tetrahedral cages (pore fixed size of 8.6 Å); (C) Crystal structure of MOF-804 with octahedral cages (pore fixed size of 12.6 Å) and tetrahedral cages (pore fixed size of A).

FIG. 4A-B provides examples of incorporating triangle linkers with extended 6-c. Zr₆O₄(OH)₄(HCOO)₆(CO₂)₆ SBUs. (A) Crystal structures of MOF-777 and MOF-778 (isomorphous Hf version of MOF-777) in which hexagonal SBUs and the trigonal planar organic linking moiety forms kgd-layers bridged by formate into 3D tfz-d net; and (B) Perpendicular perinterpenetration of kgd-layers in MOF-778.

FIG. 5A-C provides examples of incorporating a square linker with extended 6-c. Zr₆O₈(HCOO)₆(RCOO)₆ SBUs. (A) Tetrahedral cage for a tetrahedral linker; (B) Crystal structure possessing a large adamantine-like cage; and (C) Underlying topology of the crystal structure is spn-net.

FIG. 6A-C provides examples of incorporating tetrahedral linkers with extended 8-c. Zr₆O₈(RCOO)₈ SBUs. (A) Underlying topology target of flu-net; (B) Crystal structure of MOF-841 which possess a rhombic dodecahedral cage; and (C) Crystal structure of MOF-842, an illustration of isoreticular expansion.

FIG. 7 provides a scheme to produce MOF-777 by linking hexagonal shaped zirconium building units with triangle shaped organic linking ligands.

FIG. 8A-C demonstrates the difference in connectivity for Zr-carboxylate SBUs from different MOFs. Connectivity for (A) UiO-66; (B) MOF-545; and (C) MOF-777.

FIG. 9 presents the MOF-777 framework showing the connectivity between Zr-Carboxylate SBUs and BTB linking moieties. MOF-777 [Zr₆O₄(OH)₄](HCOO)₄(OH)₂(H₂O)₄BTB₂]. Crystal system: orthorhombic. Space group: Cmcm. Unit Cell: a=34.86 Å, b=20.13 Å, c=16.77 Å.

FIG. 10 presents a diagram of the MOF-777 framework. A pore of MOF-777 having a diameter of 4.986 Å is also indicated.

FIG. 11A-C provides the crystal structure of MOF-777 from (A) top down view; (B) angled view; and (C) side view.

FIG. 12 provides a schematic showing a top down view of MOF-777's kgd-a net structure showing the connection and placement of hexagonal Zr-SBUs and trigonal planar BTB organic linking moieties.

FIG. 13A-C provides close up views showing that the MOF-777 kgd-layers are linked by formate molecules. (A) X-axis directly out of the page; (B) 10 degree angled view; and (C) 90 degree side view

FIG. 14A-E presents a graph showing (A) PXRD variation by increasing the amount of acetic acid; (B) SEM image of crystals formed by using acetic acid; (C) PXRD variation by increasing the amount of formic acid; (D) SEM image of crystals formed by using formic acid; and (E) PXRD variation by increasing amount of formic acid, and where individual peaks have been labeled.

FIG. 15 presents PXRD patterns of MOF-777 and optical microscope images of the crystals formed using the specified conditions.

FIG. 16 provides SEM images of various views of the MOF-777 framework.

FIG. 17A-B provides optical microscope images of MOF-777 using (A) low power magnification; and (B) high power magnification.

FIG. 18 shows disordered SBUs of MOF-777, where the SBUs are orientated 180° to each other.

FIG. 19 presents the as-synthesized PXRD patterns for MOF-777 versus the simulated PXRD pattern for MOF-777.

FIG. 20 presents N₂ isotherm data for MOF-777.

FIG. 21 provides a comparison of the PRXD patterns for activated MOF-777, as-synthesized MOF-777, and simulated MOF-777.

FIG. 22A-B provides thermogravimetric (TGA) data for (A) MOF-777, and (B) UiO-66 and UiO-77.

FIG. 23 provides optical microscope images of MOF-777 (top) and variation of the PXRD pattern for MOF-777 (bottom) when MOF-777 is immersed in water or methanol for 3 days.

FIG. 24 presents PXRD patterns of MOF-778 and optical microscope images of the crystals formed using the specified conditions.

FIG. 25 presents PXRD patterns and optical microscope images of MOFs comprising the indicated Hf-SBUs and organic linking moieties.

FIG. 26 presents PXRD patterns and optical microscope images of MOFs comprising the indicated Zr-SBUs and organic linking moieties.

FIG. 27 presents a scheme to synthesize MOF-801, a 12-extension Zr-carboxylate SBU. Also shown is an optical image of the octahedral crystals of MOF-801 and a depiction of the MOF-801 framework. Structural characteristics and pore sizes for MOF-801 are also indicated.

FIG. 28 provides a comparison of the experimental PXRD patterns of MOF-801(SC): as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 29 provides a comparison of the experimental PXRD patterns of MOF-801(P): as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 30 provides a comparison of the experimental PXRD patterns of MOF-801: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 31 presents a N₂ isotherm of MOF-801(P) at 77 K.

FIG. 32 presents a N₂ isotherm of MOF-801(SC) at 77 K.

FIG. 33 presents a N₂ isotherm of activated MOF-801 at 77 K. The surface area is of MOF-801 is also indicated.

FIG. 34 presents a TGA trace for as-prepared MOF-801(SC), heating rate: 5° C. min⁻¹ in air.

FIG. 35 presents a TGA trace for as-prepared MOF-801(P), heating rate: 5° C. min⁻¹ in air.

FIG. 36 presents a TGA trace for as-prepared MOF-801, heating rate: 5° C. min⁻¹ in air. The TGA analysis indicates that MOF-801 is stable up to 400° C.

FIG. 37 provides SEM images of as synthesized MOF-801 (top) and activated MOF-801 (bottom). The small pores seen on the surface of activated MOF-801 are due to solvent molecules escaping during activation.

FIG. 38 provides a comparison of the experimental PXRD patterns for a large scale bulk sample of MOF-801: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 39 demonstrates the water resistant properties of MOF-801 by comparing the PXRD patterns of experimental MOF-801 (top) after being immersed in water for 24 hours with the simulated pattern (bottom) from single-crystal X-ray data.

FIG. 40 provides for the cycle performance of water uptake in MOF-801(P) at 298 K. The sample was evacuated for 2 h at 298 K between the cycles.

FIG. 41 presents a scheme to synthesize MOF-802, a 10-extension Zr-carboxylate SBU. Also shown is an optical image of the crystals of MOF-802 and a depiction of the MOF-802 framework. The structural characteristics of MOF-802, btc net topology, and ball and stick model for the 10-extension SBU is further presented.

FIG. 42 provides a comparison of the experimental PXRD patterns for MOF-802: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 43 presents a H₂ isotherm of MOF-802 at 77 K. The pores of MOF-802 (˜4 Å) are too small for a N₂ sorption measurement at 77 K.

FIG. 44 presents a TGA trace for as-prepared MOF-802, heating rate: 5° C. min⁻¹ in air.

FIG. 45 provides for the cycle performance of water uptake in MOF-802 at 298 K. The sample was evacuated for 2 h at 298 K between the cycles.

FIG. 46 presents a scheme to synthesize MOF-803, an 8-extension Zr-carboxylate SBU. Also shown is an optical image of the crystals of MOF-803 and a depiction of the MOF-803 framework. The structural characteristics of MOF-803, reo-a net topology, and ball and stick model for the 8-extension SBU is further presented.

FIG. 47 provides a comparison of the experimental PXRD patterns for MOF-803: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 48 provides that MOF-803 can be partially activated by heating under vacuum, while can be fully activated by using super-critical CO₂ procedure and heating under vacuum.

FIG. 49 presents a H₂ isotherm of MOF-803 at 77 K and 87 K.

FIG. 50 provides a sorption curve for H₂ by MOF-803. Q_st=7.05 kJ/mol at zero uptake.

FIG. 51 presents a N₂ isotherm of MOF-803 at 77 K.

FIG. 52 provides for the cycle performance of water uptake in MOF-803 at 298 K. The sample was evacuated for 2 h at 298 K between the cycles.

FIG. 53 presents a scheme to synthesize MOF-804, an OH functionalized Zr-carboxylate SBU. Also shown are a depiction of the MOF-803 framework and the structural characteristics of MOF-803.

FIG. 54 presents a N₂ isotherm of MOF-804 at 77 K.

FIG. 55 provides a comparison of H₂ isotherms for MOF-804 and MOF-75 (Mg) at 77 K, and MOF-804 at 87 K.

FIG. 56 provides a sorption curve for H₂ by MOF-804. Q_st=8.45 kJ/mol at zero uptake.

FIG. 57 provides absorbance uptake curves for CO₂, N₂ and CH₄ by MOF-804 at 298 K, 283 K, and 273 K under increasing gas pressures.

FIG. 58 provides a sorption curve for CO₂ by MOF-804. Q_st(CO₂)=30.2 kJ/mol at zero uptake.

FIG. 59 provides for cycle performance of water uptake in MOF-804 at 298 K. The sample was evacuated for 2 h at 298 K between the cycles.

FIG. 60 presents a scheme to synthesize MOF-805. A depiction of the MOF-805 framework is also shown.

FIG. 61 provides a comparison of the experimental PXRD patterns for MOF-805: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 62 presents a N₂ isotherm of MOF-805 at 77 K.

FIG. 63 presents a TGA trace for as-prepared MOF-805, heating rate: 5° C. min⁻¹ in air.

FIG. 64 provides for the cycle performance of water uptake in MOF-805 at 298 K. The sample was evacuated for 2 h at 298 K between the cycles.

FIG. 65 presents a scheme to synthesize MOF-806. Also shown is an optical image of the crystals of MOF-806 and a depiction of the MOF-806 framework.

FIG. 66 provides a comparison of the experimental PXRD patterns for MOF-806: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 67 presents a N₂ isotherm of MOF-806 at 77 K.

FIG. 68 provides a TGA trace for as-prepared MOF-806, heating rate: 5° C. min⁻¹ in air.

FIG. 69 provides for the cycle performance of water uptake in MOF-806 at 298 K. The sample was evacuated for 2 h at 298 K between the cycles.

FIG. 70 presents a scheme to synthesize MOF-807. Also shown is a depiction of the MOF-807 framework.

FIG. 71 presents a scheme to synthesize MOF-808. Also shown is a depiction of the MOF-808 framework and a close up of the 6c-extension of the SBU. The structural characteristics of MOF-808 and spn-a net topology is further presented.

FIG. 72 presents a N₂ isotherm of MOF-808 at 77 K.

FIG. 73 provides a TGA trace for as-prepared MOF-808, heating rate: 5° C. min⁻¹ in air.

FIG. 74 provides for the cycle performance of water uptake in MOF-808 at 298 K. The sample was evacuated for 2 h at 298 K between the cycles.

FIG. 75 presents a scheme to synthesize MOF-812, a Zr-carboxylate SBU based upon a tetrahedral linker. Also shown is a depiction of the MOF-812 framework. The structural characteristics of MOF-812, ith-a net topology, and ball and stick model for the 12-c cuboctahedron SBU is further presented.

FIG. 76 provides a comparison of the experimental PXRD patterns of MOF-812: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 77 presents a scheme to synthesize MOF-841, a Zr-carboxylate SBU based upon a tetrahedral linker. Also shown is an optical image of the crystals of MOF-841 and a depiction of the MOF-841 framework. The structural characteristics of MOF-841 and the flu-a net topology is further presented.

FIG. 78 provides a comparison of the experimental PXRD patterns of MOF-841: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 79 presents a N₂ isotherm of MOF-841 at 77 K.

FIG. 80 presents a N₂ isotherm of activated MOF-841 at 77 K.

FIG. 81 provides a comparison of H₂ isotherms of MOF-841, MOF-74 (Mg) and MOF-177 at 77 K.

FIG. 82 provides a comparison of H₂ isotherms of MOF-841, MOF-74 (Mg) and MOF-177 at ambient temperature.

FIG. 83 presents a TGA trace for as-prepared MOF-841, heating rate: 5° C. min⁻¹ in air.

FIG. 84 presents a TGA trace for as-prepared MOF-841 and activated MOF-841, heating rate: 5° C. min⁻¹ in air. TGA shows that the stability of MOF-841 is at least up to 300° C.

FIG. 85 provides for the cycle performance of water uptake in MOF-841 at 298 K. The sample was evacuated for 2 h at 298 K between the cycles.

FIG. 86 presents a scheme to synthesize MOF-842, a Zr-carboxylate SBU based upon a tetrahedral linker. Also shown is an optical image of the crystals of MOF-842 and a depiction of the MOF-842 framework.

FIG. 87 presents a scheme to synthesize MOF-867, a Zr-carboxylate SBU based upon a linker which can be metallized. Also shown is a depiction of the MOF-867 framework.

FIG. 88 provides a comparison of the experimental PXRD patterns for MOF-867: as-prepared (top) and simulated pattern (bottom) from single-crystal X-ray data.

FIG. 89 provides that formate molecules in MOFs with Zr-SBUs can be replaced with sulfate molecules upon treatment with aqueous hydrogen sulfuric acid.

FIG. 90 provides PXRD patterns of MOF-808 treated with various molar concentrations of H₂SO₄ indicating that the MOF-808 framework is resistant and structurally stable up to 1.0M H₂SO₄.

FIG. 91 presents N₂ isotherm data for MOF-808 with different molar concentrations of H₂SO₄ indicating that the porosity of the framework is maintained under acidic conditions.

FIG. 92 provides IR tracings of MOF-808 and MOF-808 treated with 0.1M H₂SO₄. Extra peaks appearing at 996, 1165, 1301 cm⁻¹ corresponding to the v₃ vibrational modes of binding SO₄ groups.

FIG. 93 presents TGA analysis of MOF-808 treated with 0.1M H₂SO₄ under a nitrogen atmosphere. A small step around 300° C. is attributed to the loss of the residue formate and adsorption of water. A big step at 500° C. correlates to the decomposition of the framework.

FIG. 94 provides N₂ isotherms for MOF-808 treated with 0.1M H₂SO₄ at various temperatures. When the sample was activated at a temperature higher than 300° C. a decrease in N₂ uptake was detected indicating the collapse of the framework with a corresponding color change of the framework from white to black.

FIG. 95 provides an illustration of the zirconium-carboxylate SBU of MOF-808 that has been treated with 0.1M H₂SO₄. Sulfate molecules bound to the SBU is indicated (top). A close up of a bound sulfate molecule (bottom). Electron density indicates that coordinate sites which were previously occupied by formate anions are occupied by SO₄ groups having two orientations. Roughly there are 3 SO₄ per SBU based upon site occupancy.

DETAILED DESCRIPTION

As used herein and in the appended claims, the singular forms “a,” “and,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an organic linking ligand” includes a plurality of such linking ligands and reference to “the metal ion” includes reference to one or more metal ions and equivalents thereof known to those skilled in the art, and so forth.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art. Although many methods and reagents similar or equivalent to those described herein, the exemplary methods and materials are presented herein.

Also, the use of “or” means “and/or” unless stated otherwise. Similarly, “comprise,” “comprises,” “comprising” “include,” “includes,” and “including” are interchangeable and not intended to be limiting.

It is to be further understood that where descriptions of various embodiments use the term “comprising,” those skilled in the art would understand that in some specific instances, an embodiment can be alternatively described using language “consisting essentially of” or “consisting of.”

All publications mentioned herein are incorporated herein by reference in full for the purpose of describing and disclosing the methodologies, which are described in the publications, which might be used in connection with the description herein. The publications discussed above and throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior disclosure.

The term “alkyl”, refers to an organic group that is comprised of carbon and hydrogen atoms that contain single covalent bonds between carbons. Typically, an “alkyl” as used in this disclosure, refers to an organic group that contains 1 to 30 carbon atoms, unless stated otherwise. Where if there is more than 1 carbon, the carbons may be connected in a linear manner, or alternatively if there are more than 2 carbons then the carbons may also be linked in a branched fashion so that the parent chain contains one or more secondary, tertiary, or quaternary carbons. An alkyl may be substituted or unsubstituted, unless stated otherwise.

The term “alkenyl”, refers to an organic group that is comprised of carbon and hydrogen atoms that contains at least one double covalent bond between two carbons. Typically, an “alkenyl” as used in this disclosure, refers to organic group that contains 1 to 30 carbon atoms, unless stated otherwise. While a C₁-alkenyl can form a double bond to a carbon of a parent chain, an alkenyl group of three or more carbons can contain more than one double bond. It certain instances the alkenyl group will be conjugated, in other cases an alkenyl group will not be conjugated, and yet other cases the alkenyl group may have stretches of conjugation and stretches of nonconjugation. Additionally, if there is more than 1 carbon, the carbons may be connected in a linear manner, or alternatively if there are more than 3 carbons then the carbons may also be linked in a branched fashion so that the parent chain contains one or more secondary, tertiary, or quaternary carbons. An alkenyl may be substituted or unsubstituted, unless stated otherwise.

The term “alkynyl”, refers to an organic group that is comprised of carbon and hydrogen atoms that contains a triple covalent bond between two carbons. Typically, an “alkynyl” as used in this disclosure, refers to organic group that contains 1 to 30 carbon atoms, unless stated otherwise. While a C₁-alkynyl can form a triple bond to a carbon of a parent chain, an alkynyl group of three or more carbons can contain more than one triple bond. Where if there is more than 1 carbon, the carbons may be connected in a linear manner, or alternatively if there are more than 4 carbons then the carbons may also be linked in a branched fashion so that the parent chain contains one or more secondary, tertiary, or quaternary carbons. An alkynyl may be substituted or unsubstituted, unless stated otherwise.

The term “cycloalkyl”, as used in this disclosure, refers to an alkyl that contains at least 3 carbon atoms but no more than 12 carbon atoms connected so that it forms a ring. A “cycloalkyl” for the purposes of this disclosure encompass from 1 to 12 cycloalkyl rings, wherein when the cycloalkyl is greater than 1 ring, then the cycloalkyl rings are joined so that they are linked, fused, or a combination thereof. A cycloalkyl may be substituted or unsubstituted, or in the case of more than one cycloalkyl ring, one or more rings may be unsubstituted, one or more rings may be substituted, or a combination thereof.

The term “cycloalkenyl”, as used in this disclosure, refers to an alkene that contains at least 3 carbon atoms but no more than 12 carbon atoms connected so that it forms a ring. A “cycloalkenyl” for the purposes of this disclosure encompass from 1 to 12 cycloalkenyl rings, wherein when the cycloalkenyl is greater than 1 ring, then the cycloalkenyl rings are joined so that they are linked, fused, or a combination thereof. A cycloalkenyl may be substituted or unsubstituted, or in the case of more than one cycloalkenyl ring, one or more rings may be unsubstituted, one or more rings may be substituted, or a combination thereof.

The term “aryl”, as used in this disclosure, refers to a conjugated planar ring system with delocalized pi electron clouds that contain only carbon as ring atoms. An “aryl” for the purposes of this disclosure encompass from 1 to 12 aryl rings wherein when the aryl is greater than 1 ring the aryl rings are joined so that they are linked, fused, or a combination thereof. An aryl may be substituted or unsubstituted, or in the case of more than one aryl ring, one or more rings may be unsubstituted, one or more rings may be substituted, or a combination thereof.

The term “heterocycle”, as used in this disclosure, refers to ring structures that contain at least 1 noncarbon ring atom. A “heterocycle” for the purposes of this disclosure encompass from 1 to 12 heterocycle rings wherein when the heterocycle is greater than 1 ring the heterocycle rings are joined so that they are linked, fused, or a combination thereof. A heterocycle may be a hetero-aryl or nonaromatic, or in the case of more than one heterocycle ring, one or more rings may be nonaromatic, one or more rings may be hetero-aryls, or a combination thereof. A heterocycle may be substituted or unsubstituted, or in the case of more than one heterocycle ring one or more rings may be unsubstituted, one or more rings may be substituted, or a combination thereof. Typically, the noncarbon ring atom is N, O, S, Si, Al, B, or P. In case where there is more than one noncarbon ring atom, these noncarbon ring atoms can either be the same element, or combination of different elements, such as N and O. Examples of heterocycles include, but are not limited to: a monocyclic heterocycle such as, aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, imidazolidine, pyrazolidine, pyrazoline, dioxolane, sulfolane 2,3-dihydrofuran, 2,5-dihydrofuran tetrahydrofuran, thiophane, piperidine, 1,2,3,6-tetrahydro-pyridine, piperazine, morpholine, thiomorpholine, pyran, thiopyran, 2,3-dihydropyran, tetrahydropyran, 1,4-dihydropyridine, 1,4-dioxane, 1,3-dioxane, dioxane, homopiperidine, 2,3,4,7-tetrahydro-1H-azepine homopiperazine, 1,3-dioxepane, 4,7-dihydro-1,3-dioxepin, and hexamethylene oxide; and polycyclic heterocycles such as, indole, indoline, isoindoline, quinoline, tetrahydroquinoline, isoquinoline, tetrahydroisoquinoline, 1,4-benzodioxan, coumarin, dihydrocoumarin, benzofuran, 2,3-dihydrobenzofuran, isobenzofuran, chromene, chroman, isochroman, xanthene, phenoxathiin, thianthrene, indolizine, isoindole, indazole, purine, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, phenanthridine, perimidine, phenanthroline, phenazine, phenothiazine, phenoxazine, 1,2-benzisoxazole, benzothiophene, benzoxazole, benzthiazole, benzimidazole, benztriazole, thioxanthine, carbazole, carboline, acridine, pyrolizidine, and quinolizidine. In addition to the polycyclic heterocycles described above, heterocycle includes polycyclic heterocycles wherein the ring fusion between two or more rings includes more than one bond common to both rings and more than two atoms common to both rings. Examples of such bridged heterocycles include quinuclidine, diazabicyclo[2.2.1]heptane and 7-oxabicyclo[2.2.1]heptane.

The terms “heterocyclic group”, “heterocyclic moiety”, “heterocyclic”, or “heterocyclo” used alone or as a suffix or prefix, refers to a heterocycle that has had one or more hydrogens removed therefrom.

The term “hetero-” when used as a prefix, such as, hetero-alkyl, hetero-alkenyl, hetero-alkynyl, or hetero-hydrocarbon, for the purpose of this disclosure refers to the specified hydrocarbon having one or more carbon atoms replaced by non-carbon atoms as part of the parent chain. Examples of such non-carbon atoms include, but are not limited to, N, O, S, Si, Al, B, and P. If there is more than one non-carbon atom in the hetero-based parent chain then this atom may be the same element or may be a combination of different elements, such as N and O.

The term “mixed ring system” refers to optionally substituted ring structures that contain at least two rings, and wherein the rings are joined together by linking, fusing, or a combination thereof. A mixed ring system comprises a combination of different ring types, including cycloalkyl, cycloalkenyl, aryl, and heterocycle.

The term “unsubstituted” with respect to hydrocarbons, heterocycles, and the like, refers to structures wherein the parent chain contains no substituents.

The term “substituted” with respect to hydrocarbons, heterocycles, and the like, refers to structures wherein the parent chain contains one or more substituents.

The term “substituent” refers to an atom or group of atoms substituted in place of a hydrogen atom. For purposes of this disclosure, a substituent would include deuterium atoms.

The term “hydrocarbons” refers to groups of atoms that contain only carbon and hydrogen. Examples of hydrocarbons that can be used in this disclosure include, but are not limited to, alkanes, alkenes, alkynes, arenes, and benzyls.

The term “functional group” or “FG” refers to specific groups of atoms within molecules that are responsible for the characteristic chemical reactions of those molecules. While the same functional group will undergo the same or similar chemical reaction(s) regardless of the size of the molecule it is a part of, its relative reactivity can be modified by nearby functional groups. The atoms of functional groups are linked to each other and to the rest of the molecule by covalent bonds. Examples of FG that can be used in this disclosure, include, but are not limited to, substituted or unsubstituted alkyls, substituted or unsubstituted alkenyls, substituted or unsubstituted alkynyls, substituted or unsubstituted aryls, substituted or unsubstituted hetero-alkyls, substituted or unsubstituted hetero-alkenyls, substituted or unsubstituted hetero-alkynyls, substituted or unsubstituted cycloalkyls, substituted or unsubstituted cycloalkenyls, substituted or unsubstituted hetero-aryls, substituted or unsubstituted heterocycles, halos, hydroxyls, anhydrides, carbonyls, carboxyls, carbonates, carboxylates, aldehydes, haloformyls, esters, hydroperoxy, peroxy, ethers, orthoesters, carboxamides, amines, imines, imides, azides, azos, cyanates, isocyanates, nitrates, nitriles, isonitriles, nitrosos, nitros, nitrosooxy, pyridyls, sulfhydryls, sulfides, disulfides, sulfinyls, sulfos, thiocyanates, isothiocyanates, carbonothioyls, phosphinos, phosphonos, phosphates, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄, AsO₃H, AsO₄H, P(SH)₃, and As(SH)₃.

The term “acidic site precursor” or “acid site precursor” as used herein refers to ligands possessing functional groups capable of becoming Bronsted and/or Lewis acids. Further, “acidic site precursors” can be used in preparing strong solid-acid MOFs (sa-MOFs). Examples of acidic site precursors, include but are not limited to, F⁻, Cl⁻, ClO⁻, ClO₂⁻, ClO₃⁻, ClO₄⁻, Br⁻, BrO⁻, I⁻, IO₃⁻, IO₄⁻, NO₃⁻, S₂⁻, HS⁻, HSO₃⁻, SO₃²⁻, SO₄²⁻, HSO₄⁻, H₂PO₄²⁻, PO₄³⁻, CO₃²⁻, HCO₃⁻, H₃BO₃⁻, SiO₃²⁻, PF₆⁻ and organic acid anions, such as CF₃CO₂⁻ and CF₃SO₃⁻.

As used herein, a wavy line intersecting another line that is connected to an atom indicates that this atom is covalently bonded to another entity that is present but not being depicted in the structure. A wavy line that does not intersect a line but is connected to an atom indicates that this atom is interacting with another atom by a bond or some other type of identifiable association.

Metal-organic frameworks (MOFs) are porous crystalline materials that are constructed by linking metal clusters called Secondary Binding Units (SBUs) and organic linking moieties. MOFs have high surface area and high porosity which enable them to be utilized in diverse fields, such as gas storage, catalysis, and sensors. However, MOFs which are chemically and thermally stable are rare. Further, very few MOFs have been reported to be water resistant and thus capable of absorbing water. Accordingly, MOFs have been generally restricted in their use to gaseous environments and mild environmental conditions (i.e., at temperatures less than 50° C.). However, many industrial and environmental processes are performed under much harsher and variable environments that utilize not only high heat but also solvents.

MOFs comprised of SBUs that comprise metal, metal ions, or metal containing complexes that can form very strong bonds with oxygen atoms from carboxylate based organic linking moieties having specific geometries were found to have high thermal stabilities and resistance to solvents and acids. Accordingly, the MOFs of the disclosure are capable of being utilized under harsh reaction conditions and environments. For example, the MOFs disclosed herein can serve as adsorbents in adsorptive heat transformation processes using aqueous or organic solvents; as proton conducting materials in acidic environments; as strong solid-acid materials; and as catalysts in high temperature and high pressure industrial processes.

The synthesis methods provided herein allow for the production of single-crystal MOFs that are large enough to be characterized by X-ray diffraction, and are generally applicable to allow for the characterization of many new types MOFs which comprise various metals, and linkers varying by length, shapes/geometry, and/or functionality. The syntheses methods disclosed herein allow for control over the extension (e.g., 12, 10, 8, 6 and 4) of metal-carboxylate SBU clusters and can produce MOFs with linear ditopic organic linking moieties, bent ditopic organic linking moieties, tritopic organic linking moieties, square organic linking moieties or tetrahedral organic linking moieties. The MOFs of the disclosure can comprise multivariate metal ratios and functionalities in order to tune the MOFs to have specific adsorption proprieties and pore dynamics. The MOFs of the disclosure are related by being thermal, solvent and/or acid resistant.

Further, due to the acid resistant properties of the MOFs disclosed herein, the MOFs of the disclosure can be synthesized as strong solid-acids, or be modified post synthesis to be strong solid-acids. Strong solid-acids are important catalytic materials that can be used in various industries. For example, solid acid catalysis is heavily used in oil refining and the chemical industry. Although in most cases the nature of the active sites of solid acids are known and its chemical behavior can be modeled or theorized, industries can benefit from solid acid materials that have higher efficiencies, selectivities, stabilities, and environmental friendliness as well as having lower costs. The MOFs disclosed herein are ideally suited as solid-acid substrates. The MOFs acid resistant properties along with a highly ordered structure provide a platform to study and simulate sites for acid precursor incorporation. Moreover, by using various organic linking moieties and metal ions, the MOFs disclosed herein are highly tunable and can be tailored so as to provide suitable solid-acid catalytic environments for particular applications. For example, the solid-acid MOFs (sa-MOFs) disclosed herein can be used to catalyze a variety of reactions including alkylations, isomerizations, condensations, etherifications, acylations, esterifications, nitrations, oligomerizations, Fischer-Tropsch reactions, cracking, and methane oxidative coupling reactions.

In a particular embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprising a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is an organic linking ligand comprising an optionally substituted (C₁-C₂₀) alkyl, optionally substituted (C₁-C₂₀) alkenyl, optionally substituted (C₁-C₂₀) alkynyl, optionally substituted (C₁-C₂₀) hetero-alkyl, optionally substituted (C₁-C₂₀) hetero-alkenyl, optionally substituted (C₁-C₂₀) hetero-alkynyl, optionally substituted (C₃-C₁₂) cycloalkyl, optionally substituted (C₃-C₁₂) cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle or optionally substituted mixed ring system, wherein the linking ligand comprises at least two or more carboxylate linking clusters.

In a certain embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is an organic linking ligand comprising one or more structures of Formula I-XII:

wherein,

A¹-A⁸ are independently a C, N, O, or S;

A⁹ is selected from

X¹-X⁸ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and

R¹-R¹⁶ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system. It should be noted that a carboxylate is depicted in embodiments of the linking ligands depicted herein. These carboxylates undergo condensation with, e.g., a metal or metal ion to form a M-O bond, wherein M is the metal or metal ion and O is the oxygen of the carboxylate.

In another embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is a linear diptopic organic linking ligand comprising one or more structures of Formula V-VII:

wherein,

R³⁷-R⁵⁴ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system.

In yet another embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is a linear diptopic organic linking ligand comprising one or more structures of Formula V(a), VI(a), VI(b) and VII(a):

In a particular embodiment, MOFs disclosed herein are based upon extending a 12-carbon cuboctahedral X₆(μ₃-O/OH)₈(COO)₁₂ clusters (where X is a metal ion) with linear ditopic linkers, resulting in 3D frameworks which possess tetrahedral cages and octahedral cages in fcu net topology.

In an alternate embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is a bent diptopic organic linking ligand comprising one or more structures of Formula VIII-XV:

wherein,

A⁴-A⁸ are independently a C, N, O, or S;

A⁹ is selected from

X⁴-X⁸ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and

R⁵⁵-R¹⁰² are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system.

In a further embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is a bent diptopic organic linking ligand comprising one or more structures of Formula VIII(a), VIII(b), VIII(c), VIII(d), VIII(e), VIII(f), VIII(g), VIII(h), IX(a), X(a), XI(a), XII(a). XIII(a), XIV(a), XV(a), XV(b), and XV(c):

In another embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is an organic linking ligand comprising a tetratopic organic linking ligand comprising one or more structures of Formula XVI-XXII:

wherein,

R²⁵-R³⁶, R⁵⁵-R⁵⁸, R⁶⁰, R⁶¹, R⁶³, R⁶⁴, R¹⁰³-R¹⁸⁶ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system.

In a further embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is an organic linking ligand comprising a tetratopic organic linking ligand comprising one or more structures of Formula XVI(a), XVII(a), XVIII(a), XIX(a), XX(a), XXI(a) and XXII(a):

In another embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), a MOF of the disclosure comprises a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is a tritopic organic linking ligand having one or more structures of Formula I-IV:

wherein,

A¹-A³ are independently a C, N, O, or S;

X¹-X³ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and

R¹-R³⁶ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system.

In yet another embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), a MOF of the disclosure comprises a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is a tritopic organic linking ligand comprising one or more structures of any one of Formula I-IV:

wherein,

A¹-A³ are independently a C, N, O, or S;

X¹-X³ are independently selected from H, D, optionally substituted FG, optionally substituted (C₁-C₂₀)alkyl, optionally substituted (C₁-C₁₉)heteroalkyl, optionally substituted (C₁-C₂₀)alkenyl, optionally substituted (C₁-C₁₉)heteroalkenyl, optionally substituted (C₁-C₁₉)alkynyl, optionally substituted (C₁-C₁₉)heteroalkynyl, optionally substituted (C₁-C₁₉)cycloalkyl, optionally substituted (C₁-C₁₉)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, wherein one or more adjacent R groups can be linked together to form one or more substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; and

R¹, R³-R⁵, R⁷-R⁹, R¹-R¹³, R¹⁵-R¹⁷, R¹⁹-R²¹, R²³-R²⁵, R²⁷-R²⁹, R³¹-R³³, R³⁵-R³⁶ are H; and

R², R⁶, R¹⁰, R¹⁴, R¹⁸, R²², R²⁶, R³⁰ and R³⁴ are independently selected from amino, methyl, hydroxyl, ═O, ═S, halo, optionally substituted aryl, optionally substituted aryloxy, alkoxy, —O—(CH₂)_n—CH₃, and —O—(CH₂)₂—O—CH₂—CH₃, wherein n is an integer from 2 to 5.

In yet another embodiment, the disclosure provides for thermal, acid, and/or solvent resistant metal organic frameworks comprised of a plurality of linked M-O-L secondary binding units (SBUs), a MOF of the disclosure comprises a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is a tritopic organic linking ligand comprising one or more structures of Formula I(a), II(a), III(a) and IV(a):

The disclosure further provides for thermal, acid, and/or solvent resistant MOFs that are based on tfz-d type 3D topology resulting from stacking kgd-type 2D structures of hexagonal M-O-L SBUs linked to trigonal planar tritopic organic ligands. In a further embodiment, MOFs disclosed herein have a tfz-d type 3D topology resulting from stacking kgd-type 2D structures of hexagonal M-O-L SBUs linked to trigonal planar tritopic organic ligands having a structure of Formula I-IV. In yet a further embodiment, the thermal, acid, and solvent resistant metal organic frameworks disclosed herein have a tfz-d type 3D topology resulting from stacking kgd-type 2D structures of hexagonal M-O-L SBUs linked to trigonal planar tritopic organic ligands having a structure of Formula I(a), II(a), III(a), or IV(a).

MOFs based on M-O-L SBUs linked to trigonal planar tritopic organic ligands (e.g., MOF-777) have a layer-like topology that allows for exfoliation of layers. So far, very few MOFs have been reported that can exfoliate layers, and most of these MOF either have no apertures or are not stable under ambient conditions. The layers of the kgd-type 2D structures are connected together via interactions with linking anions. For the purpose of this disclosure, “linking anions” are anionic molecules which can form a bond with one or more SBUs so as connect two or more SBUs together in a stacking like arrangement. Examples of “linking anions,” include but are not limited to, formate, acetate, phthalate, lactate, oxalate, citrate, fumurate, adipate, anthranilate, ascorbate, benzoate, butyrate, lactate, malate, malonate, tatrate, succinate, sorbate, cinnamate, glutamate, gluconate, propionate, pavalate, and valerate. In a particular embodiment, MOFs comprising kgd-type 2D structures are connected together with linking anions to form 3D MOFs with tfz-d topology (e.g., MOF-777).

In a certain embodiment, one or more metals and/or metal ions, that can be used in the (1) synthesis of a thermal, acid, and/or solvent resistant MOF of the disclosure, (2) exchanged post synthesis of the MOF disclosed herein, and/or (3) added to a MOF disclosed herein by forming coordination complexes with post framework reactant linking clusters, include, but are not limited to, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁺, Hf³⁺, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²⁺, Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr, Mo⁶⁺, Mo⁵⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W²⁺, W⁺, W, Mn⁷⁺, Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺, Re²⁺, Re⁺, Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺, Os²⁺, Os⁺, Os, Co⁵⁺, Co⁴⁺, Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺, Ir⁴⁺, Ir³⁺, Ir²⁺, Ir⁺, Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺, Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag³⁺, Ag²⁺, Ag⁺, Au⁵⁺, Au⁴⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺, B²⁺, B⁺, Al³⁺, Al²⁺, Al⁺, Ga³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In³⁺, Tl³⁺, Tl⁺, Si⁴⁺, Si³⁺, Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶⁺, Te⁵⁺, Te⁴⁺, Te²⁺, La³⁺, La²⁺, Ce⁴⁺, Ce³⁺, Ce²⁺, Pr⁴⁺, Pr³⁺, Pr²⁺, Nd³⁺, Nd²⁺, Sm³⁺, Sm²⁺, Eu³⁺, Eu²⁺, Gd³⁺, Gd²⁺, Gd⁺, Tb⁴⁺, Tb³⁺, Tb²⁺, Tb⁺, Db³⁺, Db²⁺, Ho³⁺, Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺, Yb³⁺, Yb²⁺, Lu³⁺, and combinations thereof, including any complexes which contain the metals or metal ions listed above, as well as any corresponding metal salt counter-anions.

In a further embodiment, one or more metal ions, that can be used in the (1) synthesis of a thermal, acid, and/or solvent resistant MOF of the disclosure, (2) exchanged post synthesis of the MOF disclosed herein, and/or (3) added to a MOF disclosed herein by forming coordination complexes with post framework reactant linking clusters, include, but are not limited to, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁺, Hf³⁺, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²⁺, Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr, Mo⁶⁺, Mo⁵⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W⁺, W, Mn⁷⁺, Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺, Re²⁺, Re⁺, Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺, Os²⁺, Os⁺, Os, Co⁵⁺, Co⁴⁺, Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺, Ir⁴⁺, Ir³⁺, Ir²⁺, Ir⁺, Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺, Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag³⁺, Ag²⁺, Ag⁺, Au⁵⁺, Au⁴⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺, B²⁺, B⁺, Al³⁺, Al²⁺, Al⁺, Ga³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In¹⁺, Tl³⁺, Tl⁺, Si⁴⁺, Si³⁺, Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, and combinations thereof, including any complexes which contain the metal ions listed, as well as any corresponding metal salt counter-anions.

In another embodiment, one or more metal ions, that can be used in the (1) synthesis of a thermal, acid, and/or solvent resistant MOF of the disclosure, (2) exchanged post synthesis of the MOF disclosed herein, and/or (3) added to a MOF disclosed herein by forming coordination complexes with post framework reactant linking clusters, include, but are not limited to, Mg²⁺, Ca²⁺, Al³⁺, Al²⁺, Al⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁺, Hf³⁺, and combinations thereof, including any complexes which contain the metal ions listed, as well as any corresponding metal salt counter-anions.

In yet another embodiment, one or more metal ions, that can be used in the (1) synthesis of a thermal, acid, and/or solvent resistant MOF of the disclosure, (2) exchanged post synthesis of the MOF disclosed herein, and/or (3) added to a MOF disclosed herein by forming coordination complexes with post framework reactant linking clusters, include, but are not limited to, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁺, Hf³⁺, and combinations thereof, including any complexes which contain the metal ions, as well as any corresponding metal salt counter-anions.

In a preferred embodiment, one or more metal ions that can be used in the synthesis of a thermal, acid, and/or solvent resistant MOF of the disclosure comprise Zr³⁺, Zr²⁺, Hf⁺, Hf³⁺, and combinations thereof, including any complexes which contain the metal ions, as well as any corresponding metal salt counter-anions.

The MOFs of the disclosure may be generated by first utilizing a plurality of linking moieties having different functional groups, wherein at least one of these functional groups may be modified, substituted, or eliminated with a different functional group post-synthesis of the framework. In other words, at least one linking moiety comprises a functional group that may be post-synthesized reacted with a post framework reactant to further increase the diversity of the functional groups of the MOFs disclosed herein.

After MOFs of the disclosure are synthesized, the MOFs may be further modified by reacting with one or more post framework reactants that may or may not have denticity. In a certain embodiment, the MOFs as-synthesized are not reacted with a post framework reactant. In another embodiment, the MOFs as-synthesized are reacted with at least one post framework reactant. In yet another embodiment, the MOFs as-synthesized are reacted with at least two post framework reactants. In a further embodiment, the MOFs as-synthesized are reacted with at least one post framework reactant that will result in adding denticity to the framework.

The disclosure provides for chemical reactions that modify, substitute, or eliminate a functional group post-synthesis of a MOF disclosed herein with a post framework. These chemical reactions may use one or more similar or divergent chemical reaction mechanisms depending on the type of functional group and/or post framework reactant used in the reaction. Examples of chemical reaction include, but are not limited to, radical-based, unimolecular nuclephilic substitution (SN1), bimolecular nucleophilic substitution (SN2), unimolecular elimination (E1), bimolecular elimination (E2), E1cB elimination, nucleophilic aromatic substitution (SnAr), nucleophilic internal substitution (SNi), nucleophilic addition, electrophilic addition, oxidation, reduction, cycloadition, ring closing metathesis (RCM), pericylic, electrocylic, rearrangement, carbene, carbenoid, cross coupling, and degradation.

All the aforementioned linking moieties that possess appropriate reactive functionalities can be chemically transformed by a suitable reactant post framework synthesis to add further functionalities to the pores. By modifying the organic links within the framework post-synthetically, access to functional groups that were previously inaccessible or accessible only through great difficulty and/or cost is possible and facile.

It is yet further contemplated by this disclosure that to enhance chemoselectivity it may be desirable to protect one or more functional groups that would generate unfavorable products upon a chemical reaction desired for another functional group, and then deprotect this protected group after the desired reaction is completed. Employing such a protection/deprotection strategy could be used for one or more functional groups.

Other agents can be added to increase the rate of the reactions disclosed herein, including adding catalysts, bases, and acids.

In another embodiment, a post framework reactant adds at least one effect to a MOF of the disclosure including, but not limited to, modulating the gas storage ability of the MOF; modulating the sorption properties of the MOF; modulating the pore size of the MOF; modulating the catalytic activity of the MOF; modulating the conductivity of the MOF; and modulating the sensitivity of the MOF to the presence of an analyte of interest. In a further embodiment, a post framework reactant adds at least two effects to the MOF of the disclosure including, but not limited to, modulating the gas storage ability of the MOF; modulating the sorption properties of the MOF; modulating the pore size of the MOF; modulating the catalytic activity of the MOF; modulating the conductivity of the MOF; and modulating the sensitivity of the MOF to the presence of an analyte of interest.

In one embodiment, a post framework reactant can be a saturated or unsaturated heterocycle.

In another embodiment, a post framework reactant has 1-20 carbons with functional groups including atoms such as N, S, and O.

In yet another embodiment, a post framework reactant is selected to modulate the size of the pores of the MOF disclosed herein.

In another embodiment, a post framework reactant is selected to increase the hydrophobicity of the MOF disclosed herein.

In yet another embodiment, a post framework reactant is selected to modulate gas separation of the MOF disclosed herein. In a certain embodiment, a post framework reactant creates an electric dipole moment on the surface of the MOF of the disclosure when it chelates a metal ion.

In a further embodiment, a post framework reactant is selected to modulate the gas sorption properties of the MOF of the disclosure. In another embodiment, a post framework reactant is selected to promote or increase greenhouse gas sorption of the MOF disclosed herein. In another embodiment, a post framework reactant is selected to promote or increase hydrocarbon gas sorption of the MOF of the disclosure.

In yet a further embodiment, a post framework reactant is selected to increase or add catalytic efficiency to the MOF disclosed herein.

In another embodiment, a post framework reactant is selected so that organometallic complexes can be tethered to the MOF of the disclosure. Such tethered organometallic complexes can be used, for example, as heterogeneous catalysts.

The MOFs disclosed herein may be modified to be strong solid-acids, by (1) modifying linking anions used to synthesize the frameworks with acidic site precursors capable of becoming Bronstead and/or Lewis acids (e.g., sulfate, and halide anions); (2) complexing open metal sites or other portions (e.g., pore) of the MOFs disclosed herein with acidic site precursors; and (3) exchanging anions coordinated to the metal, metal ions, or metal containing complexes of the MOFs with acidic site precursors. Further, due to the highly adsorptive nature of the MOFs disclosed herein, MOFs that are strong solid-acids are capable of being superacids. In a particular embodiment, a post framework reactant is an acid site precursor.

In a particular embodiment, the MOFs of the disclosure can be used for catalysis, adsorption and separation, energy gas storage (e.g., hydrogen, methane and other natural gases), greenhouse gas capture, respirator against toxic gas/vapor, adsorptive thermal battery, water supply and purification, proton conductor, photovoltaic device, and radioactive ion capture.

In one embodiment of the disclosure, a gas storage or separation material comprising a MOF of the disclosure is provided. Advantageously, the MOF includes one or more sites for storing and/or separating gas molecules. Gases that may be stored in the gas storage material of the disclosure include gas molecules which have high electron density for attachment to the one or more sites on the surface area of a pore or interpenetrating porous network. Such electron density includes molecules having multiple bonds between two atoms contained therein or molecules having a lone pair of electrons. Suitable examples of such gases include, but are not limited to, the gases comprising a component selected from the group consisting of ammonia, argon, carbon dioxide, carbon monoxide, hydrogen, and combinations thereof. In a particularly useful variation the gas storage material is a hydrogen storage material that is used to store hydrogen (H₂). In another particularly useful variation, the gas storage material is a carbon dioxide storage material that may be used to separate carbon dioxide from a gaseous mixture.

The disclosure provides an apparatus and method for separating one or more components from a multi-component gas using a separation system having a feed side and an effluent side separated by a MOF of the disclosure. The MOF may comprise a column separation format.

In an embodiment of the disclosure, a gas storage material comprising a MOF is provided. Gases that may be stored or separated by the methods, compositions and systems of the disclosure includes gas molecules comprising available electron density for attachment to the one or more sites. Such electron density includes molecules having multiple bonds between two atoms contained therein or molecules having a lone pair of electrons. Suitable examples of such gases include, but are not limited to, the gases comprising ammonia, argon, carbon dioxide, carbon monoxide, hydrogen, and combinations thereof. In particularly useful variation, the gas binding material is a carbon dioxide binding material that may be used to separate carbon dioxide from a gaseous mixture. Moreover, the MOFs of disclosure can be used in methods or in devices that have gases or gaseous mixtures that are at temperatures between 50° C. to 525° C., 100° C. to 500° C., 150° C. to 450° C., 200° C. to 400° C., or 250° C. to 350° C.; or at temperatures greater than 50° C., 65° C., 80° C., 100° C., 120° C., 150° C., 200° C., 300° C., or greater than 400° C.

In an embodiment, a gas separation material comprising one or more MOFs disclosed herein is provided. Advantageously, a MOF disclosed herein includes one or more open metal sites for sorption of one or more select gas molecules resulting in separation of these gas molecules from a multicomponent gas. Furthermore, gases that may be separated by one or more MOFs disclosed herein include gas molecules that have available electron density for attachment to the one or more open metal sites on the surface area of a pore or interpenetrating porous network. Such electron density includes molecules having multiple bonds between two atoms contained therein or molecules having a lone pair of electrons. Suitable examples of such gases include, but are not limited to, the gases comprising ammonia, argon, carbon dioxide, hydrogen sulfide, carbonyl sulfide, carbon disulfide, mercaptans, carbon monoxide, hydrogen, and combinations thereof. In a particular embodiment, one or more MOFs disclosed herein, can be used to separate one or more component gases from a multi-component gas mixture. In a certain embodiment, one or more MOFs disclosed herein can be used to separate one or more gases with high electron density from a gas mixture. In another embodiment, one or more MOFs disclosed herein can be used to separate one or more gases with high electron density from one or more gases with low electron density.

In a particular embodiment, one or more MOFs disclosed herein are part of a device. In another embodiment, a gas separation device comprises one or more MOFs of the disclosure. In a further embodiment, a gas separation device used to separate one or more component gases from a multi-component gas mixture comprises one or more MOFs disclosed herein. Examples of gas separation and/or gas storage devices include, but are not limited to, purifiers, filters, scrubbers, pressure swing adsorption devices, molecular sieves, hollow fiber membranes, ceramic membranes, cryogenic air separation devices, and hybrid gas separation devices. In a certain embodiment, a gas separation device used to separate one or more gases with high electron density from gas mixture comprises one or more MOFs of the disclosure. In a further embodiment, a gas separation device used to separate one or more gases with high electron density from one or more low density gases comprises one or more MOFs of the disclosure.

In a particular embodiment of the disclosure, a gas storage material comprises one more MOFs disclosed herein. A gas that may be stored or separated by the methods, compositions and systems of the disclosure includes gas molecules comprising available electron density for attachment to the one or more open metal sites. Such electron density includes molecules having multiple bonds between two atoms contained therein or molecules having a lone pair of electrons. Suitable examples of such gases include, but are not limited to, the gases comprising ammonia, argon, hydrogen sulfide, carbon dioxide, hydrogen sulfide, carbonyl sulfide, carbon disulfide, mercaptans, carbon monoxide, hydrogen, and combinations thereof. In particularly useful variation, a gas binding material is a carbon dioxide binding material that may be used to separate carbon dioxide from a gaseous mixture. In a particularly useful variation a gas storage material is a hydrogen storage material that is used to store hydrogen (H₂). In another particularly useful variation, a gas storage material is a carbon dioxide storage material that may be used to separate carbon dioxide from a gaseous mixture.

In yet a further embodiment, one or more MOFs disclosed herein can be used to separate and/or store one or more gases selected from the group comprising carbon monoxide, carbon dioxide, hydrogen sulfide, carbonyl sulfide, carbon disulfide, mercaptans, nitrous oxide, and ozone.

In another embodiment, one or more MOFs disclosed herein can be used to separate and/or store one or more gases selected from the group comprising carbon monoxide, carbon dioxide, hydrogen sulfide, carbonyl sulfide, carbon disulfide, and mercaptans.

In yet another embodiment, one or more MOFs disclosed herein can be used to separate and/or store carbon monoxide or carbon dioxide.

In a certain embodiment, one or more MOFs disclosed herein can be used to separate and/or store carbon dioxide.

In an embodiment, one or more MOFs disclosed herein can be used to separate and/or store hydrogen.

In another embodiment, a gas storage device comprises one or more MOFs disclosed herein. In a further embodiment, a gas storage device used to adsorb and/or absorb one or more component gases from a multi-component gas mixture comprises one or more MOFs disclosed herein. In a certain embodiment, a gas storage device used to adsorb and/or absorb one or more gases with high electron density from gas mixture comprises one or more MOFs disclosed herein. In a further embodiment, a gas storage device used to adsorb and/or absorb one or more gases with high electron density from one or more low density gases comprises one or more MOFs disclosed herein.

In a particular embodiment, the MOFs of the disclosure can be used as a porous thin film, a catalyst, or a smart membrane for gas separation. MOFs disclosed herein that are comprised of stacked layers (e.g., MOF-777) are particularly amendable as thin films or smart membranes in gas separation or gas storage devices.

In a certain embodiment, the MOFs of the disclosure can be used to store gases or other molecules in devices that operate at elevated temperatures, including at temperatures between 50° C. to 525° C., 100° C. to 500° C., 150° C. to 450° C., 200° C. to 400° C., or 250° C. to 350° C.; or at temperatures greater than 50° C., 65° C., 80° C., 100° C., 120° C., 150° C., 200° C., 300° C., or greater than 400° C.

In a another embodiment, the MOFs of the disclosure can be used to separate gases or other molecules in devices that operate at elevated temperatures, including at temperatures between 50° C. to 525° C., 100° C. to 500° C., 150° C. to 450° C., 200° C. to 400° C., or 250° C. to 350° C.; or at temperatures greater than 50° C., 65° C., 80° C., 100° C., 120° C., 150° C., 200° C., 300° C., or greater than 400° C.

In a certain embodiment, the MOFs of the disclosure can be used to store gases or other molecules in devices that operate in acidic environments, aqueous environments, or in the presence of organic solvents. In a further embodiment, the device is a water purification device, photovoltaic device, or radioactive ion capture device.

The disclosure also provides methods using MOFs disclosed herein. In a certain embodiment, a method to separate or store one or more gases comprises contacting one or more gases with one or more MOFs disclosed herein. In a further embodiment, a method to separate or store one or more gases from a mixed gas mixture comprises contacting the gas mixture with one or more MOFs disclosed herein. In yet a further embodiment, a method to separate or store one or more high electron density gases from a mixed gas mixture comprises contacting the gas mixture with one or more MOFs disclosed herein. In a certain embodiment, a method to separate or store one or more gases from a fuel gas stream comprises contacting the fuel gas stream with one or more MOFs disclosed herein. In a further embodiment, a method to separate or store one or more acid gases from a natural gas stream comprises contacting the natural gas stream with one or more MOFs disclosed herein. In yet another embodiment, a method to separate or store one or more gases from the exhaust of a combustion engine comprises contacting the exhaust with one or more MOFs disclosed herein. In a certain embodiment, a method to separate or store one or more gases from flue-gas comprises contacting the flue-gas with one or more MOFs disclosed herein. In a particular embodiment, for the methods provided herein the one or more gases are heated at temperature between 50° C. to 525° C., 100° C. to 500° C., 150° C. to 450° C., 200° C. to 400° C., or 250° C. to 350° C.; or at temperature greater than 50° C., 65° C., 80° C., 100° C., 120° C., 150° C., 200° C., 300° C., or greater than 400° C.

The MOFs of the disclosure can be used for removing contaminants from natural gas streams, including carbon dioxide, hydrogen sulfide, and water vapor. Moreover, due to the acid and water resistant properties of the MOFs disclosed herein, the MOFs of the disclosure are especially suited for natural gas separation and storage. “Natural gas” refers to a multi-component gas obtained from a crude oil well (associated gas) or from a subterranean gas-bearing formation (non-associated gas). The composition and pressure of natural gas can vary significantly. A typical natural gas stream contains methane as a significant component. The natural gas will also typically contain ethane, higher molecular weight hydrocarbons, one or more acid gases (such as carbon dioxide, hydrogen sulfide, carbonyl sulfide, carbon disulfide, and mercaptans), and minor amounts of contaminants such as water, nitrogen, iron sulfide, wax, and crude oil.

In a certain embodiment, one or more MOFs disclosed herein can be used to separate and/or store one or more gases from a natural gas stream. In another embodiment, one or more MOF disclosed herein can be used to separate and/or store one or more acid gases from a natural gas stream. In yet another embodiment, one or more MOFs disclosed herein can be used to separate and/or store one or more gases from a town gas stream. In yet another embodiment, one or more MOFs disclosed herein can be used to separate and/or store one or more gases of a biogas stream. In a certain embodiment, one or more MOFs disclosed herein can be used to separate and/or store one or more gases from a syngas stream.

Sorption is a general term that refers to a process resulting in the association of atoms or molecules with a target material. Sorption includes both adsorption and absorption. Absorption refers to a process in which atoms or molecules move into the bulk of a porous material, such as the absorption of water by a sponge. Adsorption refers to a process in which atoms or molecules move from a bulk phase (that is, solid, liquid, or gas) onto a solid or liquid surface. The term adsorption may be used in the context of solid surfaces in contact with liquids and gases. Molecules that have been adsorbed onto solid surfaces are referred to generically as adsorbates, and the surface to which they are adsorbed as the substrate or adsorbent. Adsorption is usually described through isotherms, that is, functions which connect the amount of adsorbate on the adsorbent, with its pressure (if gas) or concentration (if liquid). In general, desorption refers to the reverse of adsorption, and is a process in which molecules adsorbed on a surface are transferred back into a bulk phase.

MOFs of the disclosure can be used as standard compounds for sorption instruments, and obtained results would be helpful to improve various industrial plants (i.e. separation or recovery of chemical substance).

In a variation of this embodiment, the gaseous storage site comprises a MOF with a pore which has been functionalized with a group having a desired size or charge. In a refinement, this activation involves removing one or more chemical moieties (guest molecules) from the MOF disclosed herein. Typically, such guest molecules include species such as water, solvent molecules contained within the MOF disclosed herein, and other chemical moieties having electron density available for attachment.

The MOFs used in the embodiments of the disclosure include a plurality of pores for gas adsorption. In one variation, the plurality of pores has a unimodal size distribution. In another variation, the plurality of pores have a multimodal (e.g., bimodal) size distribution.

The disclosure further provides for catalyst comprising a MOF of the disclosure (e.g., sa-MOFs). The MOFs disclosed herein, as crystalline material, layered material, or as molding, can be used in the catalytic conversion of organic molecules. Reactions of this type are, for example, oxidations, the epoxidation of olefins, e.g. the preparation of propylene oxide from propylene and H₂O₂ the hydroxylation of aromatics, e.g. the preparation of hydroquinone from phenol and H₂O₂ or the conversion of toluene into cresol, the conversion of alkanes into alcohols, aldehydes and acids, isomerization, reactions, for example the conversion of epoxides into aldehydes.

The following examples are intended to illustrate but not limit the disclosure. While they are typical of those that might be used, other procedures known to those skilled in the art may alternatively be used.

Examples

Materials

Formic acid (purity >98%) was obtained from either Aldrich Chemical Co. or from EMD Millipore Chemicals. N,N-Dimethylformamide (DMF), and anhydrous methanol were obtained from EMD Millipore Chemicals; anhydrous acetone was obtained from Acros Organics; zirconium oxychloride octahydrate (ZrOCl₂.8H₂O, purity ≧99.5%) and Sigmacote® siliconizing reagent were obtained from Sigma-Aldrich Co. Fumaric acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid [H₂BDC—(OH)₂], 3,3′-dihydroxy-4,4′-biphenyldicarboxylic acid [H₂BPDC—(OH)₂], thiophene-2,5-dicarboxylic acid (H₂TDC), 1H-pyrazole-3,5-dicarboxylic acid (H₂PZDC), hafnium tetrachloride (HfCl₄), acetic acid, and N,N-dimethylformamide (DEF) were purchased from Aldrich Chemical Co. obtained from Aldrich. 1,3,5-benzenetricarboxylic acid (H₃BTC) was obtained from either Aldrich Chemical Co. or from EMD Millipore Chemicals. 1,5-Dihydroxynaphthalene-2,6-dicarboxylic acid [H₂NDC—(OH)₂] was purchased from Sugai Chemical Industry (Japan). 4,4′,4″,4′″-Methanetetrayltetrabenzoic acid (H₄MTB) was prepared according to the published procedure (Si). 4,4′-[(2,5-Dimethoxy-1,4-phenylene)bis(ethyne-2,1-diyl)] dibenzoic acid [H₂-PEDB—(OMe)₂] was kindly provided by Prof Stoddart group at Northwestern University. All starting materials and solvents, unless otherwise specified, were used without further purification.

General Procedure for Sample Preparation for MOF-801, MOF-802, MOF-803, MOF-804, MOF-805, MOF-806, MOF-807, MOF-808, MOF-812, MOF-841, MOF-842, and MOF-867:

To reduce nucleation in the growth of MOF single-crystals, the inner surface of glass containers were rinsed with Sigmacote® siliconizing reagent, washed three times with acetone, and dried in oven before use. Solvent exchange of the MOFs is performed by immersing the sample in anhydrous methanol or acetone for three days, during which the solvent was decanted and freshly replenished three times per day. For supercritical CO₂ activation, the solvent-exchanged MOFs were fully exchanged with liquid CO₂, kept under supercritical CO₂ atmosphere, and then bled using a Tousimis Samdri PVT-3D critical point dryer.

X-Ray Diffraction Analysis:

Single-crystal X-ray diffraction (SXRD) data were typically collected on a Bruker D8-Venture diffractometer equipped with Mo- (λ=0.71073 Å) and Cu-target (λ=1.54184 Å) micro-focus X-ray tubes and a PHOTON 100 CMOS detector, unless indicated otherwise. Additional data was collected using synchrotron radiation in the beamline 11.3.1 of the Advanced Light Source, LBNL.

Powder X-ray diffraction patterns (PXRD) were recorder using a Bruker D8 Advance diffractometer (Göbel-mirror monochromated Cu Kα radiation λ=1.54056 Å). Room-temperature neutron powder diffraction data were collected on the high-resolution neutron powder diffractometer, BT1, at the National Institute of Standards and Technology (NIST) Center for Neutron Research using a Ge(311) monochromator (λ=2.0781 Å) and a 60 minute collimator.

Nuclear Magnetic Resonance (NMR) and Elemental Mircoanalysis (EA) Analysis:

Solution ¹H NMR spectra were acquired on a Bruker AVB-400 NMR spectrometer. EA were performed in the Microanalytical Laboratory of the College of Chemistry at UC Berkeley, using a Perkin Elmer 2400 Series II CHNS elemental analyzer. Attenuated total reflectance (ATR) FTIR spectra of neat samples were performed in-house on a Bruker ALPHA Platinum ATR-FTIR Spectrometer equipped with a single reflection diamond ATR module.

Thermal Gravimetric Analysis:

TGA curves were recorded in-house on a TA Q500 thermal analysis system under air flow.

Isotherm Analysis:

Low-pressure gas (N₂ and Ar) adsorption isotherms were recorded in-house on a Quantachrome Autosorb-1 volumetric gas adsorption analyzer. Liquid nitrogen and argon baths were used for the measurements at 77 and 87 K, respectively. Water isotherms were measured in-house on a BEL Japan BELSORP-aqua3, and the water uptake in weight percent (wt %) unit is calculated as [(adsorbed amount of water)/(amount of adsorbent)×100], consistent with the established procedures. Prior to the water adsorption measurements, water (analyte) was flash frozen under liquid nitrogen and then evacuated under dynamic vacuum at least five times to remove any gases in the water reservoir. The measurement temperature was controlled with a water circulator. Helium was used for the estimation of dead space for gas and water adsorption measurements. Ultra-high-purity grade N₂, Ar, and He gases (Praxair, 99.999% purity) were used throughout the experiments.

Synthesis of MOF-777 [Zr₆O₄(OH)₄](HCOO)₄(H₂O)₂(OH)₂ BTB₂

In 20 mL vial, zirconium dichloride oxide octahydrate (12 mg, 0.037 mmol) and 1,3,5-tris(4-carboxyphenyl)benzene (H₃BTB, 10 mg, 0.023 mmol) were added to N,N-dimethylformamide (DMF, 4 mL). The solution was sonicated for ten minutes. Following the sonication, formic acid (2.5 mL) was added to the solution. The solution was heated at 130° C. in preheated oven for five days. The single crystals were collected and washed with DMF (5×10 mL) over three hour period. The DMF solvent was then replaced with methanol (9×20 mL) over three days period. The methanol was then removed in vacuo (30 mTorr) for 48 hrs.

Synthesis of Hf-MOF-777 [Hf₆O₄(OH)₄](HCOO)₄(OH)₂(H₂O)₂ BTB₂

In 20 mL vial, hafnium dichloride (12 mg, 0.037 mmol) and 1,3,5-tris(4-carboxyphenyl)benzene (H₃BTB, 10 mg, 0.023 mmol) were added to N,N-dimethylformamide (DMF, 4 mL). The solution was sonicated for ten minutes. Following the sonication, formic acid (2.5 ml) was added to the solution. The solution was heated at 130° C. in preheated oven for five days. The single crystals were collected and washed with DMF (5×10 mL) over three hour period. The DMF solvent was then replaced with methanol (9×20 mL) over three days period. The methanol was then removed in vacuo (30 mTorr) for 48 hrs.

Single Crystal Sample of Zr₆O₄(OH)₄(Fumarate)₆, MOF-801-SC.

A solvent mixture of fumaric acid (0.081 g, 0.70 mmol) and ZrOCl₂.8H₂O (0.23 g, 0.70 mmol) in a solvent mixture of DMF/formic acid (35 mL/5.3 mL) were placed in a 60-mL screw-capped glass jar, which was heated at 120° C. for one day. Octahedral colorless crystals were collected and quickly washed three times with 5 mL of fresh DMF (Yield: 0.10 g; 63% based on fumaric acid). ¹H digested solution NMR of as-synthesized sample (400 MHz, DMSO-d₆, ppm): 8.103 (s, 0.5H, 0.5×HCOOH), 7.917 (s, 1H, 1×DMF), 6.621 (s, 2H, 1× Fumarate), 2.871 (s, 3H, 1×DMF), 2.714 (s, 3H, 1×DMF). EA of as-synthesized sample: Calcd. for [Zr₆O₄(OH)₄(C₄H₂O₄)₆](C₃H₇NO)₆(HCOOH)₃ (H₂O)₁₀: C, 25.49; H, 3.99; N, 3.96%. Found: C, 25.22; H, 3.19; N, 3.95%. ATR-FTIR (4000-400 cm⁻¹): 3151 (br), 1651 (m), 1566 (s), 1384 (s), 1200 (w), 1098 (w), 1062 (w), 984 (m), 793 (m), 739 (w), 640 (s), 483 (s).

As-synthesized MOF-801-SC was rinsed three times per day with 10 mL of DMF for three days and immersed in 10 mL of anhydrous methanol for three days, during which time the solvent was replaced three times per day. The solid was then evacuated at 150° C. for 24 hours to yield activated sample. EA of activated sample: Calcd. for Zr₆C₂₄H₂₈O₃₈=[Zr₆O₄(OH)₄(C₄H₂O₄)₆](H₂O)₆: C, 19.59; H, 1.92%. Found: C, 19.40; H, 1.77%. ATR-FTIR (4000-400 cm⁻¹): 3217 (br), 1574 (m), 1397 (s), 1212 (w), 983 (w), 795 (w), 653 (s), 490 (m).

Microcrystalline Powder Sample of Zr₆O₄(OH)₄(Fumarate)₆, MOF-801-P.

Fumaric acid (5.8 g, 50 mmol) and ZrOCl₂.8H₂O (16 g, 50 mmol) were dissolved in a solvent mixture of DMF/formic acid (200 mL/70 mL) in a 500-mL screw-capped jar, which was heated at 130° C. for 6 hours. The resulting white precipitate was filtrated using Nylon membrane filters (pore size 0.2-μm), and washed three times with 20 mL of fresh DMF and three times with 50 mL of methanol (Yield: 10 g; 90% based on fumaric acid). As-synthesized MOF-801-P was rinsed three times per day with 50 mL of DMF for three days, and immersed in 100 mL methanol for three days, during which time the methanol was replaced three times per day. The solid was then evacuated at 150° C. for 24 hours to yield activated sample. EA of activated sample: Calcd. for Zr₆C₂₄H₂₈O₃₈=[Zr₆O₄(OH)₄(C₄H₂O₄)₆](H₂O)₆: C, 19.59; H, 1.92%. Found: C, 19.25; H, 1.05%.

Zr₆O₄(OH)₄(PZDC)₅(HCOO)₂(H₂O)₂, MOF-802

1H-Pyrazole-3,5-dicarboxylic acid (H₂PZDC) (0.27 g, 1.5 mmol) and ZrOCl₂.8H₂O (0.40 g, 1.3 mmol) in a solvent mixture of DMF/formic acid (50 mL/35 mL) were placed in a 125-mL screw-capped glass jar, which was heated at 130° C. for three days. Block colorless crystals were collected and washed three times with 5 mL of fresh DMF (Yield: 0.12 g; 39% based on H₂PZDC). ¹H digested solution NMR of as-synthesized sample (400 MHz, DMSO-d₆, ppm): 8.108 (s, 1H, 1×HCOOH), 7.924 (s, 0.8H, 0.8×DMF), 7.086 (s, 1H, 1×PZDC), 2.871 (s, 2.4H, 0.8×DMF), 2.714 (s, 2.4H, 0.8×DMF). EA of as-synthesized sample: Calcd. for Zr₆C₄₂H₆₆O₅₀N₁₄=[Zr₆O₄(OH)₄(C₅H₂N₂O₄)₅(HCOO)₂(H₂O)₂](C₃H₇NO)₄(HCOOH)₃(H₂O)₆: C, 23.86; H, 3.15; N, 9.27%. Found: C, 23.52; H, 3.34; N, 9.18%. ATR-FTIR (4000-400 cm⁻¹): 3082 (br), 1653 (m), 1566 (s), 1503 (m), 1463 (m), 1432 (m), 1363 (s), 1196 (m), 1097 (m), 1059 (w), 996 (m), 865 (w), 823 (w), 780 (m), 739 (w), 649 (s), 598 (m), 537 (m), 475 (s).

As-synthesized MOF-802 was rinsed three times per day with 10 mL of DMF for three days, and immersed in 10 mL of anhydrous acetone for three days, during which time the solvent was replaced three times per day. Acetone-exchanged material was activated with a supercritical CO₂ activation protocol and evacuated at 120° C. for 24 hours to yield activated sample. EA of activated sample: Calcd. for Zr₆C₂₇H₂₀O₃₄N₁₀=[Zr₆O₄(OH)₄(C₅H₂N₂O₄)₅(HCOO)₂(H₂O)₂]: C, 20.58; H, 1.28; N, 8.89%. Found: C, 18.39; H, 0.72; N, 7.56%. ATR-FTIR (4000-400 cm⁻¹): 2870 (vw), 1656 (w), 1557 (m), 1462 (w), 1434 (w), 1360 (s), 1187 (w), 1095 (w), 1015 (w), 989 (w), 817 (w), 798 (w), 778 (w), 758 (w), 737 (w), 645 (s), 543 (w), 470 (s).

Zr₆O₄(OH)₄(TDC)₄(HCOO)₄, MOF-803

Benzene-1,2,4-tricarboxylic acid (H₂TDC) (0.069 g, 0.40 mmol) and ZrOCl₂.8H₂O (0.19 g, 0.60 mmol) in a solvent mixture of DMF/formic acid (20 mL/11 mL) were placed in a 60-mL screw-capped glass jar, which was heated at 130° C. for three days. Cubic colorless crystals were collected and washed three times with 10 mL of fresh DMF (Yield: 0.11 g, 73% based on H₂TDC). ¹H digested solution NMR of activated sample (400 MHz, DMSO-d₆, ppm): 8.110 (s, 1H, 1×HCOOH), 7.927 (s, 2H, 2×DMF), 7.697 (s, 2H, 1×TDC), 2.873 (s, 6H, 2×DMF), 2.716 (s, 6H, 2×DMF). EA of as-synthesized sample: Calcd. for Zr₆C₅₂H₈₈O₄₈N₈S₄=[Zr₆O₄(OH)₄(C₆H₂O₄S)₄ (HCOO)₄](C₃H₇NO)₈ (H₂O)₈: C, 27.53; H, 3.91; N, 4.94; S, 5.65%. Found: C, 27.72; H, 4.01; N, 4.52; S, 5.34%. ATR-FTIR (4000-400 cm⁻¹): 3270 (br), 2928 (vw), 2859 (vw), 1650 (m), 1591 (m), 1562 (m), 1527 (m), 1436 (w), 1374 (s), 1252 (m), 1097 (m), 1061 (w), 1026 (w), 848 (w), 801 (w), 767 (s), 740 (m), 685 (m), 642 (s), 475 (s).

As-synthesized MOF-803 was rinsed three times per day with 10 mL of DMF for three days, and immersed in anhydrous acetone for three days, during which time the acetone was replaced three times per day. The acetone exchanged material then underwent a supercritical CO₂ activation protocol and evacuated at 120° C. for 24 hours to yield activated sample. EA of activated sample: Calcd. for Zr₆C₂₈H₂₆O₃₇S₄=[Zr₆O₄(OH)₄(C₆H₂O₄S)₄(HCOO)₄](H₂O)₅: C, 20.63; H, 1.61, S, 7.87%. Found: C, 20.51; H, 1.27; S, 7.12%. ATR-FTIR (4000-400 cm⁻¹): 3233 (br), 1558 (m), 1527 (m), 1373 (s), 1323 (s), 1212 (w), 1125 (w), 1028 (w), 839 (w), 765 (s), 685 (m), 646 (s), 511 (m), 456 (s).

Zr₆O₄(OH)₄(BDC—(OH)₂)₆, MOF-804

2,5-Dihydroxy-terephthalic acid (H₂BDC—(OH)₂) (0.040 g, 0.20 mmol) and ZrOCl₂.8H₂O (0.064 g, 0.20 mmol) in a solvent mixture of DMF/formic acid (10 mL/4 mL) were placed in a 20-mL screw-capped glass vial, which was heated at 120° C. for one day. Yellow precipitate was then obtained by centrifuge, and washed with three times with 5 ml of fresh DMF (Yield: 0.051 g; 80% based on H₂BDC—(OH)₂). ¹H digested solution NMR of as-synthesized sample (400 MHz, DMSO-d₆, ppm): 8.106 (s, 0.3H, 0.3×HCOOH), 7.923 (s, 2H, 2×DMF), 7.267 (s, 2H, 1×BDC—(OH)₂), 2.871 (s, 6H, 2×DMF), 2.714 (s, 6H, 2×DMF). EA of as-synthesized sample: Calcd. for Zr₆C₈₆H₁₄₄O₇₄N₁₂=[Zr₆O₄(OH)₄(C₈H₄O₆)₆](C₃H₇NO)₁₂(HCOOH)₂(H₂O)₁₄: C, 33.56; H, 4.72; N, 5.46%. Found: C, 32.53; H, 4.69; N, 5.77%. ATR-FTIR (4000-400 cm⁻¹): 3258 (br), 2931 (vw), 2873 (vw), 1651 (s), 1591 (s), 1487 (m), 1456 (m), 1382 (s), 1231 (s), 1099 (m), 1061 (w), 1002 (w), 904 (w), 868 (m), 806 (m), 788 (s), 654 (vs), 610 (m), 570 (s), 480 (s).

As-synthesized MOF-804 was rinsed three times per day with 10 mL of DMF for three days and exchanged solvent with anhydrous methanol for three days, during which time the methanol was replaced three times per day. The methanol exchanged material was then evacuated at 120° C. for 24 hours to yield activated sample. EA of activated sample: Calcd. for Zr₆C₄₈H₄₈O₅₄=[Zr₆O₄(OH)₄(C₈H₄O₆)₆](H₂O)₁₀: C, 28.31; H, 2.38%. Found: C, 28.01; H, 1.91%. ATR-FTIR (4000-400 cm⁻¹): 3256 (br), 1586 (m), 1489 (m), 1457 (s), 1382 (s), 1234 (s), 1119 (w), 870 (w), 805 (m), 788 (m), 659 (s), 608 (m), 572 (s), 481 (s).

Zr₆O₄(OH)₄[NDC—(OH)₂]₆, MOF-805

1,5-Dihydroxy-naphthalene-2,6-dicarboxylic acid (H₂NDC—(OH)₂) (0.012 g, 0.050 mmol) and ZrOCl₂.8H₂O (0.032 g, 0.10 mmol) in a solvent mixture of DMF/formic acid (10 mL/2 mL) were placed in a 20-mL screw-capped glass vial, which was heated at 120° C. for one day. Yellow precipitate was then obtained by centrifuge, and washed three times with 3 mL of fresh DMF [Yield: 0.014 g, 78% based on H₂NDC—(OH)₂]. ¹H digested solution NMR of activated sample (400 MHz, DMSO-d₆, ppm): 8.109 (s, 0.25H, 0.25×HCOOH), 7.926 (s, 3H, 3×DMF), 7.811 (d, J=4.4 Hz, 2H, 1×NDC—(OH)₂), 7.732 (d, J=4.4 Hz, 2H, 1×NDC—(OH)₂), 2.872 (s, 9H, 3×DMF), 2.715 (s, 9H, 3×DMF). EA of as-synthesized sample: Calcd. for Zr₆C_127.5H₂₀₉O₈₅N₁₈=[Zr₆O₄(OH)₄(C₁₂H₆O₆)₆](C₃H₇NO)₁₈(HCOOH)_1.5(H₂O)₂₀: C, 39.25; H, 5.40; N, 6.46%. Found: C, 38.73; H, 5.02; N, 6.65%. ATR-FTIR (4000-400 cm⁻¹): 3139 (br), 2931 (w), 2874 (w), 1652 (s), 1581 (m), 1485 (m), 1417 (s), 1386 (m), 1334 (m), 1334 (m), 1285 (m), 1190 (m), 1095 (m), 1061 (m), 1016 (w), 896 (w), 866 (vw), 782 (s), 660 (s), 632 (s), 595 (s), 575 (w), 517 (w), 469 (s).

As-synthesized MOF-805 was rinsed three times per day with 5 mL of DMF for three days, and immersed in 5 mL of anhydrous methanol for three days, during which time the solvent was exchanged three times per day. Exchanged material was evacuated at 120° C. for 24 hours to yield activated sample. EA of activated sample: Calcd. for Zr₆C₇₂H₅₀O₄₉=[Zr₆O₄(OH)₄(C₁₂H₆O₆)₆](H₂O)₅: C, 38.49; H, 2.24%. Found: C, 38.36; H, 1.74%. ATR-FTIR (4000-400 cm⁻¹): 3153 (br), 1656 (w), 1582 (m), 1486 (m), 1420 (s), 1332 (w), 1285 (m), 1191 (m), 1101 (vw), 1025 (vw), 898 (w), 780 (s), 668 (s), 636 (m), 583 (w), 520 (w), 467 (s).

Zr₆O₄(OH)₄(BPDC—(OH)₂)₆, MOF-806

3,3′-Dihydroxy-biphenyl-4,4′-dicarboxylic acid (H₂BPDC—(OH)₂) (0.014 g, 0.050 mmol) and ZrOCl₂.8H₂O (0.032 g, 0.10 mmol) in a solvent mixture of DMF/formic acid (10 mL/2 mL) were placed in a 20-mL screw-capped glass vial, which was heated at 120° C. for two days. Octahedral colorless crystals were collected and washed three times with 3 mL of fresh DMF [Yield: 0.012 g, 62% based on H₂BPDC—(OH)₂]. ¹H digested solution NMR of as-synthesized sample (400 MHz, DMSO-d₆, ppm): 8.108 (s, 1.25H, 1.25×HCOOH), 7.926 (s, 3H, 3×DMF), 7.877-7.855 (m, 2H, 1×BPDC—(OH)₂), 7.274-7.252 (m, 4H, 1×BPDC—(OH)₂), 2.874 (s, 9H, 3×DMF), 2.716 (s, 9H, 3×DMF). EA of as-synthesized sample: Calcd. for Zr₆C_145.5H₂₂₉O₉₅N₁₈=[Zr₆O₄(OH)₄(C₁₄H₈₅O₆)₆](C₃H₇NO)₁₈(HCOOH)_7.5 (H₂O)₁₈: C, 40.66; H, 5.37; N, 5.87%. Found: C, 36.28; H, 4.83; N, 5.83%. ATR-FTIR (4000-400 cm⁻¹): 3226 (br), 2927 (vw), 2873 (vw), 1651 (m), 1604 (m), 1569 (m), 1434 (m), 1374 (s), 1314 (m), 1232 (w), 1165 (w), 1097 (m), 1062 (m), 1035 (w), 974 (w), 876 (m), 849 (vw), 785 (m), 762 (w), 707 (w), 647 (s), 614 (m), 570 (w), 478 (m), 434 (m).

As-synthesized MOF-806 was rinsed three times per day with 5 mL of DMF for three days, and immersed in 5 mL of anhydrous acetone for three days, during which time acetone was replaced three times per day. Acetone exchanged material was activated following a supercritical CO₂ activation protocol and evacuated at 120° C. for 24 hours to yield activated sample. EA of activated sample: Calcd. for Zr₆C₈₄H₇₂O₅₄=[Zr₆O₄(OH)₄(C₁₄H₈O₆)₆](H₂O)₁₀: C, 40.48; H, 2.91%. Found: C, 39.80; H, 2.34%. ATR-FTIR (4000-400 cm⁻¹): 3294 (br), 1632 (m), 1576 (s), 1507 (vw), 1487 (w), 1438 (s), 1375 (s), 1321 (w), 1224 (m), 1192 (w), 1164 (w), 1035 (w), 963 (w), 873 (m), 846 (w), 783 (s), 691 (m), 663 (s), 559 (w), 455 (s), 450 (s).

Zr₆O₄(OH)₄(BTC)₂(HCOO)₆, MOF-808

Benzene-1,3,5-tricarboxylic acid (H₃BTC) (0.11 g, 0.50 mmol) and ZrOCl₂.8H₂O (0.16 g, 0.50 mmol) in a solvent mixture of DMF/formic acid (20 mL/20 mL) were placed in a 60-mL screw-capped glass jar, which was heated at 100° C. for seven days. Octahedral colorless crystals were collected and washed three times with 10 mL of fresh DMF (Yield: 0.098 g, 70% based on Zr). ¹H digested solution NMR of as-synthesized sample (400 MHz, DMSO-d₆, ppm): 8.630 (s, 3H, 1×BTC), 8.114 (s, 2H, 2×HCOOH), 7.928 (s, 5H, 5×DMF), 2.874 (s, 15H, 5×DMF), 2.716 (s, 15H, 5×DMF). EA of as-synthesized sample: Calcd. for Zr₆C₅₂H₉₄O₄₃N₁₀=[Zr₆O₄(OH)₄(C₉H₃O₆)₂(HCOO)₄](C₃H₇NO)₁₀(H₂O)₅: C, 29.82; H, 4.52; N, 6.69%. Found: C, 29.74; H, 5.13; N, 6.69%. ATR-FTIR (4000-400 cm⁻¹): 3381 (br), 2930 (vw), 2861 (vw), 1651 (m), 1614 (m), 1573 (m), 1497 (w), 1437 (m), 1372 (s), 1252 (m), 1099 (m), 1061 (w), 940 (w), 864 (w), 802 (w), 783 (w), 756 (m), 717 (w), 702 (w), 646 (s), 569 (w), 501 (w), 477 (m), 445 (s).

As-synthesized MOF-808 was rinsed three times per day with DMF for three days, and immersed in 10 mL of anhydrous acetone for three days, during which time the acetone was replaced three times per day. Acetone exchanged material was then applied with supercritical CO₂ activation protocol and evacuated at 150° C. for 24 hours to yield activated sample. EA of activated sample: Calcd. for Zr₆C_25.5H_21.5O_33.5N_0.5=[Zr₆O₄(OH)₄(C₉H₃O₆)₂(HCOO)₆](C₃H₇NO)_0.5(H₂O): C, 21.59; H, 1.53, N, 0.49%. Found: C, 21.46; H, 1.46; N, 0.77%. ATR-FTIR (4000-400 cm⁻¹): 2867 (br), 1603 (m), 1583 (m), 1447 (m), 1379 (s), 1110 (w), 944 (w), 758 (w), 740 (w), 703 (m), 657 (s), 572 (w), 500 (m), 451 (s).

Zr₆O₄(OH)₄(MTB)₃(H₂O)₂, MOF-812

Methanetetrabenzoic acid (H₄MTB) (0.048 g, 0.1 mmol) and ZrOCl₂.8H₂O (0.064 g, 0.2 mmol) were dissolved in a solvent mixture of DMF/formic acid (10 mL/6 mL) in a 20-mL screw-capped glass vial, which was heated at 130° C. for one day.

Zr₆O₄(OH)₄(MTB)₂(HCOO)₄(H₂O)₄, MOF-841

H₄MTB (0.12 g, 0.25 mmol) and ZrOCl₂.8H₂O (0.32 g, 1.0 mmol) in a solvent mixture of DMF/formic acid (40 mL/25 mL) were placed in a 125-mL screw-capped glass jar, which was heated at 130° C. for two days. Mother liquor of the reaction mixture was separated and further heated at 130° C. for another two days. Colorless block crystals were collected and washed three times with 5 mL of fresh DMF (Yield: 0.13 g, 55% based on H₄MTB). ¹H digested solution NMR of as-synthesized sample (400 MHz, DMSO-d₆, ppm): 8.111 (s, 2H, 2×HCOOH), 7.929 (s, 5H, 5×DMF), 7.883 (d, J=4.4 Hz, 8H, 1×MTB), 7.335 (d, J=4.4 Hz, 8H, 1×MTB), 2.875 (5s, 15H, 5×DMF), 2.717 (s, 15H, 5×DMF). EA of as-synthesized sample: Calcd. for Zr₆C₉₂H₁₃₄O₅₄N₁₀=[Zr₆O₄(OH)₄(C₂₉H₁₆O₈)₂ (HCOO)₄(H₂O)₄](C₃H₇NO)₁₀(H₂O)₈: C, 39.58; H, 4.84; N, 5.02%. Found: C, 39.11; H, 4.91; N, 5.09%. ATR-FTIR (4000-400 cm⁻¹): 3382 (br), 2930 (vw), 2860 (vw), 1652 (m), 1602 (m), 1583 (m), 1564 (m), 1541 (m), 1407 (s), 1253 (m), 1191 (m), 1151 (w), 1096 (w), 1061 (w), 1017 (w), 860 (w), 837 (w), 772 (m), 743 (w), 719 (w), 695 (w), 646 (s), 523 (m), 454 (s).

As-synthesized MOF-841 was rinsed three times per day with 10 mL of DMF for three days and immersed in 10 mL of anhydrous acetone for three days, during which time the acetone was replaced three times per day. Acetone exchanged material was activated by first undergoing a supercritical CO₂ activation protocol and then being evacuated at 120° C. for 24 hours. EA of activated sample: Calcd. for Zr₆C₆₂H₄₈O₃₆=[Zr₆O₄(OH)₄ (C₂₉H₁₆O₈)₂(HCOO)₄(H₂O)₄]: C, 38.86; H, 2.52%. Found: C, 39.15; H, 2.16%. ATR-FTIR (4000-400 cm⁻¹): 2858 (vw), 1596 (m), 1559 (m), 1407 (s), 1380 (m), 1366 (m), 1336 (m), 1194 (w), 1152 (w), 1019 (w), 839 (w), 771 (m), 751 (m), 719 (m), 664 (m), 570 (w), 525 (m), 457 (s).

Powdered X-Ray Diffraction (PXRD) of MOF-777:

Single-crystal X-ray diffraction data for MOF-777 were collected at 100 K using a Bruker Platinum 200 diffractometer with synchrotron radiation (λ=0.774900 Å) at Beamline 11.3.1 at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory. Powder X-ray diffraction data were collected using Rigaku D/MAX-RB (12 KW) diffractometer at 40 kV, 100 mA for CuK_α radiation (λ=1.5406 Å). For single crystal XRD measurement, 100 μm size of MOF-777 was used and for PXRD measurement, obtained as synthesized single crystal was washed with DMF solvent and grinded for sample preparations.

N₂ Isotherms for Surface Area of MOF-777:

Low-pressure gas adsorption isotherms were carried out volumetrically. N₂ isotherm of MOF-777 was measured using a Quadrasorp (Quantachrome Instruments). A liquid nitrogen sample bath (77 K) was used for N₂ measurements. The N₂ gas was UHP grade. For measurement of the surface areas, the BET method was applied using the adsorption branches of the N₂ isotherms assuming a N₂ cross sectional area of 16.2 Ų/molecule. For activation process of MOF-777, the obtained crystals were washed with DMF for 3 days 9 times and DMF solvent was exchanged with methanol in the 20 mL vials for 3 days changing the methanol solvent 9 times. After drying the crystals at vacuum (30 mTorr) for 12 hrs, at room temperature. Finally, 98 mg of the crystals was transferred to glass tube and N₂ isotherm measurements were carried out. For the calculation of surface area correlation coefficient was 0.99997 and BET C-value was 2350.

Secondary Building Unit (SBU) of MOF-777:

Six Zr atoms are arranged in octahedron shape and four oxygen atoms are coordinated on four faces of the octahedron in tetrahedral arrangement and four hydroxyl molecules are coordinated on the other four faces of the octahedron resulting in [Zr₆O₄(OH)₄]¹²⁺ cluster. The six edges out of 12 edges of the octahedron are coordinated by carboxylate anion (COO⁻) of BTB linker in hexagonal arrangement resulting in [Zr₆O₄(OH)₄(COO)₆]⁶⁺. The rest of the 6⁺ charges is covered by four HCOO⁻ and two OH⁻ molecules resulting in Zr₆O₄(OH)₄(HCOO)₄(OH)₂(COO)₆. Finally adding four H₂O molecules, the overall topology of the SBU was obtained, Zr₆O₄(OH)₄(HCOO)₄(OH)₂(H₂O)₄(COO)₆ (e.g., see FIG. 7 and FIG. 12). The hexagonal shape of the building unit was completely unexpected as no similar structure has been previously reported for Zr-based MOFs. For example, reported Zr SBUs based on the Zr oxy/hydroxyl cluster are 12-coordinated cuboctahedron and 8-coordinated cube for UiO-66 and MOF-545, respectively. Considering that the cuboctahedron, cube and hexagon shaped SBUs are all based on a similar Zr oxy/hydroxyl cluster, the results presented herein demonstrate that Zr clusters can generate diverse SBUs with different connectivity and geometry. By removing the four carboxylate anions from the cubooctahedron SBU of UiO-66, the cube shape SBU of MOF-545 can be obtained; and by removing the six carboxylate anions from the SBU of UiO-66, the hexagonal SBU of MOF-777 can be obtained (e.g., see FIG. 8A-C). It has been proposed that the Zr oxy/hydroxyl cluster flexibility is based upon symmetrical geometry and the number of possible coordination sites, twelve. As the twelve edges of the Zr cluster octahedron are high symmetry coordination sites that allow for the carboxylate anions to coordinate to the edges with proper geometries, the cuboctahedron, cube and hexagonal topologies are possible. Since no hexagonal shaped inorganic and organic building units have reported in any MOF structure, the hexagonal SBU of MOF-777 is a very unique. Moreover, combinations with this hexagonal building unit for synthesizing MOFs would generate additional structural diversity.

3D Structure of MOF-777 Based on a Stacked 2D Layered Structure.

The structure of MOF-777 was obtained from single crystal XRD analysis. MOF-777 has a tfz-d type 3D structure. The crystal system is orthorhombic and the space group is Cmcm. Unit cell parameters are a=34.86 Å, b=20.13 Å, c=16.77 Å and a pore diameter of 4.986 Å was obtained from the calculation (e.g., see FIG. 9 and FIG. 10). The 3D structure of MOF-777 is comprised of stacked 2D layers (e.g., see FIG. 11). The 2D layers are comprised of hexagonal Zr SBUs and triangle BTB linkers having a 2D kgd-a type structure (e.g., see FIG. 12). Stacking these layers occurs through the z axis. The tfz-d type 3D structure of MOF-777 is formed by connecting the layers through z axis with formate molecules, which bind to vacant coordination sites on the Zr SBUs (e.g., see FIG. 13A-C). As can be seen in the SEM images of MOF-777, the layered structures are discernable (e.g., see FIG. 16). When the single crystal XRD data was obtained, the SBUs of MOF-777 were found to be disordered with two different orientations. The SBUs were rotated 180° to each other SBUs (e.g., see FIG. 18). To rectify this issue, SBUs were positioned so as to be adjacent to the other type of SBUs in the layer. From which, the ordered structure of MOF-777 was generated. Based upon this structure, the PXRD pattern of MOF-777 was simulated and compared with the experimental PXRD pattern of MOF-777 to confirm that the structure was equivalent. The PXRD pattern of the simulated structure was shown to be equivalent to the experimental PXRD pattern for MOF-777 (e.g., see FIG. 19).

Crystal Growth and Morphology of Single Crystals of MOF-777.

The images of single crystals of MOF-177 were obtained using an optimal microscope. The crystals were ˜100 μm in size and had a thickness ˜10 μm. The crystals were found to be homogeneous with hexagonal plate morphology (e.g., see FIG. 17A-B). In order to obtain crystals that had sufficient thickness for PXRD studies, the amount of formic acid had to be adjusted. By adding increasing amounts of formic acid, the intensity and sharpness of the peaks related to the stacking of the layers increased along with the thickness (up to ˜10 μm) of single crystals (e.g., see FIG. 14C-E). The results indicate that the thickness of the crystals can be controlled by varying the amount of formate molecules. As the layers are connected by formate molecules, the results are understandable.

One of the distinguishing characteristics of MOF-777 in comparison to other Zr-MOFs, is MOF-777's layered structure. While other Zr-MOFs have rigid 3D structures, MOF-777's 3D structure results from stacking interactions between hexagonal plate morphologies that have 2D topologies. Therefore, the unique hexagonal plate morphology of MOF-777 SBUs, combined with controllable thickness and high stability, indicate that MOF-777 can be used as a thin film. Relatively few studies have been conducted with MOF films and have been limited to the following: MOF-5, MOF-199 (HKUST-1), [Zr₂bdc₂(dabco)] (dabco=1,4-diazabicyclo[2,2,2]octane), [Mn(HCOO)], MIL-53(Fe) and MIL-88B. MOF-777 has several advantages over the MOFs mentioned above. By MOF-777 having plate shape morphology, MOF-777 is far more conducive for growing and covering the surface of substrate. MOF-777 is very stable, while the MOFs mentioned above, except for MOF-199 (HKUST-1), are known for being relatively unstable. The stability of MOF-777, therefore, provides an additional practical advantage for creating a thin film material. A 1 cm² scaled thin film material comprising MOF-777 was created on top of glass substrate.

Characterization of MOF-777 Surface Area.

Activated MOF-777 crystals were used for N₂ isotherms. The BET surface area of the activated sample was 974 m²/g and Langmuir surface area was 1096 m²/g. Those two values are quite lower than the calculated solvent accessible surface area (2330 m²/g) using a materials studio program. The experimental values are lower than the calculated surface area is due to a loss of crystallinity along z axis during activation. After the activation, the PXRD pattern of the sample was obtained and it showed that the peaks related to stacking of the layers disappeared such as (111), (311), (021), (221), (202) and (112), while the other peaks such as (200), (110), (310), and (020) remained still sharp and strong (e.g., see FIG. 20) indicating that the crystals lost the crystallinity along z axis.

Inductively Coupled Plasma (ICP) and Elemental Analysis (EA) of MOF-777.

Four measurements were carried out with four different samples. The wt % of each element of the activated samples was obtained from ICP and EA (e.g., see TABLE 1).

TABLE 1
Experimental wt % values of MOF-777 from ICP and EA.
	From EA	From ICP
wt %	C	O	H	N	S	Zr + O	Zr
1	37.36	15.75	2.730	0.059	0.015	44.51	27.51
2	38.06	15.58	2.715	0.059	0.013	43.57	27.21
3	38.77	14.81	2.657	0.065	0.009	43.68	27.42
4	38.51	14.81	2.604	0.068	0.011	43.99	28.21

All measurements showed similar values and the first row was chosen for the experimental value. The molecular formula from the experimental value, Zr₆C_60.7O_40.1H_53.7 reasonably matches with the molecular formula of MOF-777, Zr₆C₅₈O₃₈H₄₈. Although the oxygen and hydrogen ratios are slightly higher in experimental value, this discrepancy can be explained by the experimental having one or two water molecules within the pores.

Testing the Thermal and Chemical Stability of MOF-777.

A thermal stability test was carried out by using thermal gravimetric analysis (TGA). The first significant weight loss was from the evaporation of the solvent from the pores, while a second significant weight loss was around 550° C. was, indicating decomposition of the structure (e.g., see FIG. 22). This result shows that MOF-777 is thermally stable up to ˜550° C.

A chemical stability test of MOF-777 was carried out against water. The PXRD pattern of as-synthesized MOF-777 was compared against the PXRD pattern of MOF-777 immersed in water for 3 days (e.g., see FIG. 23). After MOF-777 was immersed in water for three days, the peaks related to the stacking of the layers disappeared, while the other peaks remained. Considering (200), (110) peaks were still sharp as those from the as-synthesized MOF-777 sample, the layers of MOF-777 are chemically stable against water.

MOF-777 has several interesting characteristics. Outside of MOF-777, no hexagonal shape inorganic and organic building units have been reported for MOFs. MOF-777's hexagonal building units therefore provide for new geometries for constructing MOFs. Also the layered structure enables MOF-777 to grow as thin layers. With the thermally and chemically stable properties of MOF-777 layers, this morphology of MOF-777 has an advantage to being used as porous thin film materials.

Characterization of Hf-MOF-777:

Hf-MOF-777 was obtained using similar synthesis reaction conditions as MOF-777 (e.g., see FIG. 24), but replacing HfCl₄ for ZrOCl₂. The morphology of single crystals of Hf-MOF-777 was a hexagonal plane, the same as MOF-777. Further, the PXRD pattern of Hf-MOF-777 is comparable to MOF-777. Based upon these results, the structure of Hf-MOF-777 is comparable to MOF-777.

A number of embodiments have been described herein. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of this disclosure. Accordingly, other embodiments are within the scope of the following claims.

Claims

1. A thermal, acid, and/or solvent resistant metal organic framework (MOF) comprising a plurality of linked M-O-L secondary binding units (SBUs), wherein M is a metal, metal ion, or metal containing complex; O is an oxygen atom of a carboxylate based linking cluster; and L is an organic linking ligand comprising one or more structures of Formula I-XII that undergoes condensation with the metal, metal ion or metal containing complex:

2. The MOF of claim 1, wherein L is a linear diptopic organic linking ligand comprising one or more structures of Formula V-VII that undergoes condensation with the metal, metal ion or metal containing complex:

3. The MOF of claim 2, wherein L is a linear diptopic organic linking ligand comprising one or more structures of Formula V(a), VI(a), VI(b) and VII(a) that undergoes condensation with the metal, metal ion or metal containing complex:

4. The MOF of claim 1, wherein L is a bent diptopic organic linking ligand comprising one or more structures of Formula VIII-XV that undergoes condensation with the metal, metal ion or metal containing complex:

5. The MOF of claim 4, wherein L is a bent diptopic organic linking ligand comprising one or more structures of Formula VIII(a), VIII(b), VIII(c), VIII(d), VIII(e), VIII(f), VIII(g), VIII(h), IX(a), X(a), XI(a), XII(a), XIII(a), XIV(a), XV(a), XV(b), and XV(c) that undergoes condensation with the metal, metal ion or metal containing complex:

6. The MOF of claim 4, wherein L is a tetratopic organic linking ligand comprising one or more structures of Formula XVI-XXII that undergoes condensation with the metal, metal ion or metal containing complex:

7. The MOF of claim 6, wherein L a tetratopic organic linking ligand comprising one or more structures of Formula XVI(a), XVII(a), XVIII(a), XIX(a), XX(a), XXI(a) and XXII(a) that undergoes condensation with the metal, metal ion or metal containing complex:

8. The MOF of claim 1, wherein L is a tritopic organic linking ligand having one or more structures of Formula I-IV that undergoes condensation with the metal, metal ion or metal containing complex:

9. The MOF of claim 1, wherein L is a tritopic organic linking ligand comprising one or more structures of any one of Formula I-IV that undergoes condensation with the metal, metal ion or metal containing complex:

10. The MOF of claim 9, wherein L is a tritopic organic linking ligand comprising one or more structures of Formula I(a), II(a), III(a) and IV(a) that undergoes condensation with the metal, metal ion or metal containing complex:

11. The MOF of claim 1, wherein M is a metal or metal ion selected from Li+, Na+, K+, Rb+, Cs+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Sc2+, Sc+, Y3+, Y2+, Y+, Ti4+, Ti3+, Ti2+, Zr4+, Zr3+, Zr2+, Hf4+, Hf3+, V5+, V4+, V3+, V2+, Nb5+, Nb4+, Nb3+, Nb2+, Ta5+, Ta4+, Ta3+, Ta2+, Cr6+, Cr5+, Cr4+, Cr3+, Cr2+, Cr+, Cr, Mo6+, Mo5+, Mo4+, Mo3+, Mo2+, Mo+, Mo, W6+, W5+, W4+, W3+, W2+, W+, W, Mn7+, Mn6+, Mn5+, Mn4+, Mn3+, Mn2+, Mn+, Re7+, Re6+, Re5+, Re4+, Re3+, Re2+, Re+, Re, Fe6+, Fe4+, Fe3+, Fe2+, Fe+, Fe, Ru8+, Ru7+, Ru6+, Ru4+, Ru3+, Ru2+, Os8+, Os7+, Os6+, Os5+, Os4+, Os3+, Os2+, Os+, Os, Co5+, Co4+, Co3+, Co2+, Co+, Rh6+, Rh5+, Rh4+, Rh3+, Rh2+, Rh+, Ir6+, Ir5+, Ir4+, Ir3+, Ir2+, Ir+, Ir, Ni3+, Ni2+, Ni+, Ni, Pd6+, Pd4+, Pd2+, Pd+, Pd, Pt6+, Pt5+, Pt4+, Pt3+, Pt2+, Pt+, Cu4+, Cu3+, Cu2+, Cu+, Ag3+, Ag2+, Ag+, Au5+, Au4+, Au3+, Au2+, Au+, Zn2+, Zn+, Zn, Cd2+, Cd+, Hg4+, Hg2+, Hg+, B3+, B2+, B+, Al3+, Al2+, Al+, Ga3+, Ga2+, Ga+, In3+, In2+, In1+, Tl3+, Tl+, Si4+, Si3+, Si2+, Si+, Ge4+, Ge3+, Ge2+, Ge+, Ge, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As2+, As+, Sb5+, Sb3+, Bi5+, Bi3+, Te6+, Te5+, Te4+, Te2+, La3+, La2+, Ce4+, Ce3+, Ce2+, Pr4+, Pr3+, Pr2+, Nd3+, Nd2+, Sm3+, Sm2+, Eu3+, Eu2+, Gd3+, Gd2+, Gd+, Tb4+, Tb3+, Tb2+, Tb+, Db3+, Db2+, Ho3+, Er3+, Tm4+, Tm3+, Tm2+, Yb3+, Yb2+, Lu3+, and combinations thereof, including any complexes which contain the metals or metal ions listed above, as well as any corresponding metal salt counter-anions.

12. The MOF of claim 11, wherein M is a metal or metal ion selected from Li+, Mg2+, Ca2+, Al3+, Al2+, Al+, Ti4+, Ti3+, Ti2+, Zr4+, Zr3+, Zr2+, Hf4+, Hf3+, and combinations thereof, including any complexes which contain the metal ions listed, as well as any corresponding metal salt counter-anions.

13. The MOF of claim 1, wherein the MOF is MOF-778 (hf-MOF-777).

14. The MOF of claim 12, wherein M is a zirconium metal or zirconium metal ion, including any complexes which contain zirconium, as well as any corresponding metal salt counter-anions.

15. The MOF of claim 13, wherein the plurality of linked M-O-L SBUs are zirconium carboxylate clusters that have 3-c, 4-c, 6-c, 8-c, 9-c, 10-c, or 12-c extensions.

16. The MOF of claim 14, wherein the MOF is MOF-801, MOF-802, MOF-803, MOF-804, MOF-805, MOF-806, MOF-807, MOF-808, MOF-812, MOF-841, MOF-842 or MOF-867.

17. The MOF of claim 15, wherein the plurality of linked M-O-L SBUs are hexagonal zirconium carboxylate clusters linked by benzene-tribenzoic acid (BTB)-based organic linking moieties.

18. The MOF of claim 17, wherein the MOF has tfz-d type 3D topology that is based upon the stacking of kgd-a type 2D layers.

19. The MOF of claim 18, wherein the layers are connected to each other via linking anions.

20. The MOF of claim 19, wherein the linking anions are selected from formate, acetate, phthalate, lactate, oxalate, citrate, fumurate, adipate, anthranilate, ascorbate, benzoate, butyrate, lactate, malate, malonate, tatrate, succinate, sorbate, cinnamate, glutamate, gluconate, propionate, pavalate, and valerate.

21. The MOF of claim 20, wherein the linking anion is formate.

22. The MOF of claim 17, wherein the MOF is MOF-777.

23. The MOF of claim 19, wherein the linking anions comprise acid site precursors.

24. The MOF of claim 23, wherein the acid site precursors are selected from F−, Cl−, ClO−, ClO2−, ClO3−, ClO4−, Br−, BrO−, I−, IO3−, IO4−, NO3−, S2−, HS−, HSO3−, SO32−, SO42−, HSO4−, H2PO42−, PO43−, CO32−, HCO3−, H3BO3, SiO32−, PF6−, CF3CO2− and CF3SO3−.

25. The MOF of claim 24, wherein the acid site precursor is HSO3−.

26. The MOF of claim 23, wherein the MOF is a strong solid-acid (sa-MOF).

27. A method for producing a strong solid acid MOF (sa-MOF) comprising: reacting an organic linking ligand of claim 1 with a zirconium or hafnium metal or metal ion at an elevated temperature for at least 2 hours, in the presence of an acid site precursor.

28. The method of claim 27, wherein the acid site precursor compound is selected from F−, Cl−, ClO−, ClO2−, ClO3−, ClO4−, Br−, BrO−, I−, IO3−, IO4−, NO3−, S2−, HS−, HSO3−, SO32−, SO42−, HSO4−, H2PO42−, PO43−, CO32−, HCO3−, H3BO3, SiO32−, PF6−, CF3CO2− and CF3SO3−.

29. The method of claim 27, wherein the organic linking ligand comprises a structure of Formula I(a), II(a), III(a), or IV(a) that undergoes condensation with the metal, metal ion or metal containing complex:

30. (canceled)

31. A gas storage and/or separation device comprising a MOF of claim 1.

32. A device comprising a thin film or membrane of a MOF of claim 17.

33. A catalytic device comprising a sa-MOF of claim 26.