Covalent organic frameworks with a woven structure

Description

TECHNICAL FIELD

The disclosure provides for covalent organic frameworks (COFs) that constructed from weaving a plurality of long organic threads together. In particular, the disclosure provides for the construction of woven COFS, where long organic strands are connected together in a woven pattern using organic ligands/complexes that when orientated in certain geometries are capable of reversibly binding metal ions.

BACKGROUND

Making fabric by weaving is known as one of the oldest and most enduring methods. Nevertheless, such an important design concept still needs to be emulated in extended chemical structures. Linking molecules into weaving structures would be of a great help to create materials with exceptional mechanical properties and dynamics. COFs are structures created with organic building blocks that are linked together. They are appealing because their low density and high porosity has many promising applications, such as for storing gas or for optoelectronics, but previously, synthesized COFs have been too rigid. Creating more flexible COFs, those that resemble woven fabrics, has been challenging on a molecular level.

SUMMARY

Provided herein are three-dimensional covalent organic frameworks (such as COF-505) that are comprised of helical organic threads that have been woven together at regular or periodic intervals. In a particular embodiment, the helical organic treads can be woven together by forming an imine bond between aldehyde functionalized copper(I)-bisphenanthroline tetrafluoroborate, Cu(PDB)₂(BF₄), and benzidine (BZ). The copper centers are topologically independent of the weaving within the COF structure and only serve as a weaving agent for bringing the threads into a woven pattern rather than the more commonly observed parallel arrangement. The copper(I) ions can be reversibly removed and added without loss of the COF structure, for which a ten-fold increase in elasticity accompanies its demetallation. The threads in COF-505 have many degrees of freedom for enormous deviations to take place between them, throughout the material, without undoing the weaving of the overall structure.

In a particular embodiment, the disclosure provides for a woven covalent organic framework that comprises a plurality of long organic threads that are mutually interlaced at regular intervals so as to form points-of-registry, wherein the long organic threads comprise organic linking ligands that have been covalently bound together and wherein at least some portion of the organic linking ligands further comprise heteroatoms and/or functional groups capable of coordinating a metal, metal ion or metal containing complex, and wherein the points-of-registry may be metalated to comprise coordinated metals, metal ions, or metal containing complexes, or may be de-metalated. In another embodiment, for a woven covalent organic framework disclosed herein, the points-of-registry comprise the general structure of Formula V:

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wherein, M is a metal ion, metal, or a metal complex that is bound to nitrogen atoms, or alternatively M is absent; R¹-R¹⁰are each independently selected from H, FG, (C₁-C₁₂)alkyl, substituted (C₁-C₁₂)alkyl, (C₂-C₁₂)alkenyl, substituted (C₂-C₁₂)alkenyl, (C₂-C₁₂)alkynyl, substituted (C₂-C₁₂)alkynyl, hetero-(C₁-C₁₂)alkyl, substituted hetero-(C₁-C₁₂)alkyl, hetero-(C₂-C₁₂)alkenyl, substituted hetero-(C₂-C₁₂)alkenyl, hetero-(C₂-C₁₂)alkynyl, substituted hetero-(C₂-C₁₂)alkynyl, (C₃-C₁₂)cycloalkyl, substituted (C₃-C₁₂)cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R⁵⁰)₃, —CH(R⁵⁰)₂, —CH₂R⁵, —C(R⁵¹)₃, —CH(R⁵¹), —CH₂R⁵¹, —OC(R⁵⁰)₃, —OCH(R⁵⁰)₂, —OCH₂R, OC(R⁵¹)₃, —OCH(R⁵¹), —OCH₂R⁵¹, or R¹-R¹⁰when adjacent can form a substituted or unsubstituted ring selected from the group comprising cycloalkyl, aryl and heterocycle; R¹¹-R¹⁴are each independently selected from H, D, FG, (C₁-C₃)alkyl, substituted (C₁-C₃)alkyl, hetero-(C₁-C₃)alkyl, or substituted hetero-(C₁-C₃)alkyl. R⁵⁰is selected from the group comprising FG, (C₁-C₁₂)alkyl, (C₁-C₁₂)substituted alkyl, (C₁-C₁₂)alkenyl, substituted (C₁-C₁₂)alkenyl, (C₁-C₁₂)alkynyl, substituted (C₁-C₁₂)alkynyl, hetero-(C₁-C₁₂)alkyl, substituted hetero-(C₁-C₁₂)alkyl, hetero-(C₁-C₁₂)alkenyl, substituted hetero-(C₁-C₁₂)alkenyl, hetero-(C₁-C₁₂)alkynyl, substituted hetero-(C₁-C₁₂)alkynyl; R⁵¹is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle; and FG is selected from the group consisting of halos, hydroxyls, anhydrides, carbonyls, carboxyls, carbonates, carboxylates, aldehydes, haloformyls, esters, hydroperoxy, peroxy, ethers, orthoesters, carboxamides, amines, imines, imides, azides, azos, cyanates, isocyanates, nitrates, nitrites, 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)₃, Ge(SH)₃, AsO₃H, AsO₃H, P(SH)₃, As(SH)₃, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₃, Ge(SH)₃, Sn(SH)₃, AsO₃H, AsO₃H, P(SH)₃, and As(SH)₃. In a further embodiment, M is a metal or a metal ion selected from the group consisting of 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⁺, Ir⁺, 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⁺, La³⁺, La²⁺, and La⁺. In a particular embodiment, M is a tetrahedrally coordinating metal ion or an octahedrally coordinating metal ion. In another embodiment, for a woven organic framework disclosed herein, the points-of-registry comprise the general structure of Formula V(a):

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wherein, M is a tetrahedrally coordinating metal ion. In a further embodiment, M is Cu⁺.

In another embodiment, for a woven covalent organic framework disclosed herein the points-of-registry comprise the general structure of Formula V(b):

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In a certain embodiment, the disclosure also provides for a woven covalent organic framework disclosed herein which comprises long organic helical threads comprising covalently bound alternating linking ligands, wherein the alternating linking ligands comprise linking ligands having the structure of Formula I:

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covalently bound to linking ligands comprising the structure of Formula II, III, or IV:

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wherein, R¹-R¹⁰, and R¹⁵-R⁴⁶are each independently selected from H, FG, (C₁-C₁₂)alkyl, substituted (C₁-C₁₂)alkyl, (C₂-C₁₂)alkenyl, substituted (C₂-C₁₂)alkenyl, (C₂-C₁₂)alkynyl, substituted (C₂-C₁₂)alkynyl, hetero-(C₁-C₁₂)alkyl, substituted hetero-(C₁-C₁₂)alkyl, hetero-(C₂-C₁₂)alkenyl, substituted hetero-(C₂-C₁₂)alkenyl, hetero-(C₂-C₁₂)alkynyl, substituted hetero-(C₂-C₁₂)alkynyl, (C₃-C₁₂)cycloalkyl, substituted (C₃-C₁₂)cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R⁵⁰)₃, —CH(R⁵⁰)₂, —CH₂R⁵⁰, —C(R⁵¹)₃, —CH(R⁵¹), —CH₂R⁵¹, —OC(R⁵⁰)₃, —OCH(R⁵⁰)₂, —OCH₂R⁵⁰, —OC(R⁵¹)₃, —OCH(R⁵¹), —OCH₂R⁵¹, or R¹-R¹⁰when adjacent can form a substituted or unsubstituted ring selected from the group comprising cycloalkyl, aryl and heterocycle; R¹¹-R¹⁴are each independently selected from H, D, FG, (C₁-C₃)alkyl, substituted (C₁-C₃)alkyl, hetero-(C₁-C₃)alkyl, or substituted hetero-(C₁-C₃)alkyl; R⁵⁰is selected from the group comprising FG, (C₁-C₁₂)alkyl, (C₁-C₁₂)substituted alkyl, (C₁-C₁₂)alkenyl, substituted (C₁-C₁₂)alkenyl, (C₁-C₁₂)alkynyl, substituted (C₁-C₁₂)alkynyl, hetero-(C₁-C₁₂)alkyl, substituted hetero-(C₁-C₁₂)alkyl, hetero-(C₁-C₁₂)alkenyl, substituted hetero-(C₁-C₁₂)alkenyl, hetero-(C₁-C₁₂)alkynyl, substituted hetero-(C₁-C₁₂)alkynyl; R⁵¹is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle; and FG is selected from the group consisting of halos, hydroxyls, anhydrides, carbonyls, carboxyls, carbonates, carboxylates, aldehydes, haloformyls, esters, hydroperoxy, peroxy, ethers, orthoesters, carboxamides, amines, imines, imides, azides, azos, cyanates, isocyanates, nitrates, nitrites, 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)₃, Ge(SH)₃, AsO₃H, AsO₃H, P(SH)₃, As(SH)₃, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₃, Ge(SH)₃, Sn(SH)₃, AsO₃H, AsO₃H, P(SH)₃, and As(SH)₃; LG is each independently selected from the group consisting of boronic acid, nitriles, aldehyde, amine, halide, hydroxyl, acyl halide, carboxylic acid, and acetic anhydride; and n is an integer from 1 to 10, wherein the LG groups of Formula I and the LG groups of Formula II, III, or IV are covalently bound together. In a further embodiment, the covalent bond formed between the LG groups of Formula I and the LG groups of Formula II, III, or IV, has the structure of:

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In a particular embodiment, the disclosure further provides for a woven covalent organic framework disclosed herein which comprises covalently bound alternating linking ligands, wherein the alternating linking ligands comprise linking ligands having the structure of Formula I(b):

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covalently bound to linking ligands comprising the structure of Formula II(b), III(b), or IV(b):

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wherein, n is an integer from 1 to 10; and wherein the linking ligands having the structure of Formula I(b) are covalently bound to the linking ligands having the structure of Formula II(b), III(b) or IV(b) via an imine bond:

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In another embodiment, the disclosure provides for a woven covalent organic framework that is de-metalated. In an alternate embodiment, the disclosure also provides for a woven framework that is metalated or re-metalated. In a further embodiment, a woven covalent organic framework disclosed herein exhibits a fold increase in elasticity when the woven covalent organic framework is de-metalated, where in the fold increase in elasticity between a metalated vs. de-metalated woven covalent organic framework is at least 2, 3, 4, 5, 6, 7, 8, 9, 10, or a range between any two numbers of the foregoing. In a further embodiment, the disclosure provides for a woven organic framework that has the structure and properties of COF-505. In another embodiment, the disclosure provides for a woven covalent organic framework where the points of registry comprise tetrahedrally coordinated metal ions. In a further embodiment, a woven covalent organic framework which has points of registry comprising tetrahedrally coordinated metal ions has a topology selected from pnf, qtz, and sod. In an alternate embodiment, the disclosure provides for a woven covalent organic framework where the points of registry comprise octahedrally coordinated metal ions. In a further embodiment, a woven covalent organic framework which has points of registry comprising octahedrally coordinated metal ions has a topology selected from kgm and pcu.

In a particular, embodiment the disclosure provides for a resilient material which comprising a woven covalent organic framework disclosed herein. Examples of such resilient materials include, but are not limited to shape-memory material development or biomedical applications.

The details of one or more embodiments of the disclosure are set forth in the accompanying drawings and the description below. Other features, objects, and advantages will be apparent from the description and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1A-D provides an embodiment of weaving and entanglement of structures described herein. Illustrations of weaving of threads in (A) two-dimensions, and (B) three-dimensions, compared with (C) entanglements of sheets, (D) three-dimensional arrangements. Expanded views of interlocking of rings (insets).

FIG. 2A-B provides an embodiment of a general strategy for the design and synthesis of weaving structures. COF-505 was constructed from organic threads using copper(I) as a template (A) to make an extended weaving structure (B), which can be subsequently de-metalated and re-metalated.

FIG. 3A-G presents morphology and electron microscopy studies of COF-505. (A) Crystallites aggregated on a crystalline sphere observed by SEM. (B) TEM image of a single sub-μm crystal used for 3D-EDT. (C) 2D projection of the reconstructed reciprocal lattice of COF-505 obtained at 298 K from a set of 3D-EDT data. (D) HRTEM image of COF-505 taken with the [1-10] incidence. (E) 2D projected potential map obtained by imposing pgg plane group symmetry on FIG. 1D. (F) Reconstructed 3D electrostatic potential map (threshold: 0.8). (G) Indexed PXRD pattern of the activated sample of COF-505 (black) and the Pawley fitting (gray) from the modeled structure.

FIG. 4A-D presents an embodiment of a single crystal structure of COF-505. (A) The weaving structure of COF-505 consists of chemically identical helices (as shown, helices that have opposite chirality) with the pitch of 14.2 Å. (B) Helices (top) propagate in the [1-10] direction, while the helices (bottom) propagate in the [110] direction with copper (I) ions as the points-of-registry. (C) Neighboring helices are weaved with helices having opposite chirality to form the overall framework. (D) Dark gray and medium gray helices and their C₂symmetry related lighter gray and light gray copies are mutually weaved. Additional parallel helices in (C) and (D) are omitted for clarity.

FIG. 5 presents the synthesis of the molecular analogue of COF-505, Cu(PBM)₂.

FIG. 6 provides an ORTEP drawing of the crystal structure of Cu(PBD)₂. Thermal ellipsoids are shown with 50% probability.

FIG. 7 presents a FT-IR spectrum of Cu(PBD)₂.

FIG. 8 displays a FT-IR spectrum of BZ.

FIG. 9 presents a FT-IR spectrum of molecular analogue Cu(PBM)₂.

FIG. 10 displays a FT-IR spectrum of activated COF-505.

FIG. 11 presents a stack plot of FT-IR spectra for the comparison between starting materials, molecular analogue, and activated COF-505.

FIG. 12 presents a solid-state ¹³C CP/MAS NMR spectrum of COF-505 and its molecular analogue.

FIG. 13 presents a solid-state ¹³C NMR spectrum of COF-505 before and after CPPI technique.

FIG. 14A-B displays the morphology of COF-505 by SEM. (A) Crystalline spheres from aggregated crystallites. (B) Crystal plates on the surface of a sphere.

FIG. 15 provides a comparison of experimental and calculated PXRD patterns for COF-505.

FIG. 16 presents the weaving adamantane cage of COF-505.

FIG. 17 displays an HRTEM image of a nano-crystal. The image can be explained if the crystal has the same space group symmetry with slightly different lattice constants from COF-505.

FIG. 18 provides a PXRD comparison of Cu(PDB)₂, BZ, and COF-505.

FIG. 19 provides a TGA trace for activated COF-505.

FIG. 20 provides images of vials comprising crystalline powder of COF-505 (left), de-metalated COF-505 (middle), and re-metalated COF-505 (right). The COF-505 sample changed color from dark brown to yellow as it was de-metalated and after re-metalation, the dark color was recovered.

FIG. 21 presents PXRD patterns of as-synthesized COF-505, the de-metalated and re-metalated materials. The crystallinity of COF-505 decreases upon de-metalation and can be fully restored after re-metalation with copper(I) ions.

FIG. 22 provides a FT-IR spectrum of the de-metalated COF-505.

FIG. 23 provides a FT-IR spectrum of recovered COF-505 after re-metalation.

FIG. 24 presents a SEM image of the de-metalated material, which shows similar morphology to COF-505.

FIG. 25A-D provides AFM images of the COF particles (A) before and (B) after de-metalation. Scale bar: 200 nm. Grey scale range: 240 nm. (C) The load of indentation P for COF particles before and (D) after de-metalation as a function of elastic displacement Δh.

FIG. 26 demonstrates that the same type weaving of threads observed in COF-505 can be used to make many other COFs based on common net topologies (e.g., kgm, pnf, qtz, pcu, and sod).

DETAILED DESCRIPTION

As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a linking moiety” includes a plurality of such linking moieties and reference to “the core” includes reference to one or more cores 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 to which this disclosure belongs. Although any methods and reagents similar or equivalent to those described herein can be used in the disclosed methods and compositions, the exemplary methods and materials are now described.

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 may be used in connection with the description herein. However, with respect to any similar or identical terms found in the incorporated publications and those expressly defined in this application, then the terms' definition as expressly put forth in this application shall control in all respects.

A bond indicated by a straight line and a dashed line indicates a bond that may be a single covalent bond or alternatively a double covalent bond. But in the case where an atom's maximum valence would be exceeded by forming a double covalent bond, then the bond would be a single covalent bond.

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 2 to 30 carbon atoms, unless stated otherwise. While a C₂-alkenyl can form a double bond, an alkenyl group of three or more carbons can contain more than one double bond. In 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 2 carbon, the carbon atoms may be connected in a linear manner, or alternatively if there are more than 3 carbon atoms 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 2 to 30 carbon atoms, unless stated otherwise. While a C₂-alkynyl can form a triple bond, an alkynyl group of three or more carbons can contain more than one triple bond. Where if there are more than 2 carbon atoms, the carbons may be connected in a linear manner, or alternatively if there are more than 4 carbon atoms then the carbon atoms 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 “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.

As used herein, a “core” refers to a repeating unit or units found in a network. A network can comprise a homogenous repeating core, a heterogeneous repeating core or a combination of homogenous and heterogeneous cores.

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 4 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 “framework” as used herein, refers to an ordered structure comprised of secondary building units (SBUs) that can be linked together in defined, repeated and controllable manner, such that the resulting structure is characterized as being porous, periodic and crystalline. Typically, “frameworks” are two dimensional (2D) or three dimensional (3D) structures. Examples of “frameworks” include, but are not limited to, “metal-organic frameworks” or “MOFs”, “zeolitic imidazolate frameworks” or “ZIFs”, or “covalent organic frameworks” or “COFs”. While MOFs and ZIFs comprise SBUs of metals or metal ions linked together by forming covalent bonds with linking clusters on organic linking ligands, COFs are comprised of SBUs of organic linking ligands that are linked together by forming covalent bonds via linking clusters. “Frameworks”, as used herein, are highly ordered and extended structures that are not based upon a centrally coordinated ion, but involve many repeated secondary building units (SBUs) linked together. Accordingly, “frameworks” are orders of magnitude much larger than coordination complexes, and have different structural and chemical properties due to the framework's open and ordered structure.

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 FGs that can be used in this disclosure, include, but are not limited to, 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)₃, Ge(SH)₃, AsO₃H, AsO₃H, P(SH)₃, As(SH)₃, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₃, AsO₃H, AsO₃H, P(SH)₃, and As(SH)₃.

The term “heterocycle”, as used in this disclosure, refers to ring structures that contain at least 1 non-carbon ring atom, and typically comprise from 3 to 12 ring atoms. 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 non-carbon ring atom is N, O, S, Si, Al, B, or P. In case where there is more than one non-carbon ring atom, these non-carbon 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-aryl” used alone or as a suffix or prefix, refers to a heterocycle or heterocyclyl having aromatic character. Examples of heteroaryls include, but are not limited to, pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, furazan, pyrrole, imidazole, thiazole, oxazole, pyrazole, isothiazole, isoxazole, 1,2,3-triazole, tetrazole, 1,2,3-thiadiazole, 1,2,3-oxadiazole, 1,2,4-triazole, 1,2,4-thiadiazole, 1,2,4-oxadiazole, 1,3,4-triazole, 1,3,4-thiadiazole, and 1,3,4-oxadiazole.

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 “linking group” or “LG” as used herein refers to functional groups that are found on organic linking ligands (typically, two or more LG groups) that are used to form covalent bonds with one or more additional organic linking ligands. While organic linking ligands may all comprise the same LG groups, e.g., boronic acid, typically, the FG groups differ either on the same organic linking ligand or between organic linking ligands. The linking ligands are chosen to have high selectivity's for each other under defined reaction conditions (e.g., imine bond formation, Fischer esterification, Michael additions, Schotten-Baumann Reaction, etc.). Examples of LG, include functional groups like boronic acid, nitriles, aldehydes, amines, halides, hydroxyls, acyl halides, carboxylic acids, and acetic anhydrides.

The term “linking cluster” refers to one or more atoms capable of forming an association, e.g. covalent bond, polar covalent bond, ionic bond, and Van Der Waal interactions, with one or more atoms of another linking moiety or core. For example, a linking cluster can comprise NN(H)N, N(H)NN, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₃, Ge(SH)₃, Sn(SH)₃, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, CH(RSH)₂, C(RSH)₃, CH(RNH₂)₂, C(RNH₂)₃, CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C(RCN)₃, CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₃, CH(OH)₂, C(OH)₃, CH(CN)₂, and C(CN)₃, wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group comprising 1 to 2 phenyl rings and CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₃, CH(OH)₂, C(OH)₃, CH(CN)₂, and C(CN)₃.

The term “long organic threads” as used herein refers to extended structures that comprise organic linking ligands that have been covalently linked together to form a long organic strand, where the long organic strand comprises at least 20, 30, 40, 50, or 100 organic linking ligands. Furthermore, a “long organ threads” as used herein do not refer to naturally occurring polymers like polynucleotides, polypeptides, and the like.

The term “long helical organic threads” refers to long organic threads as defined above that further have a helical twist.

A “metal” refers to a solid material that is typically hard, shiny, malleable, fusible, and ductile, with good electrical and thermal conductivity. “Metals” used herein refer to metals selected from alkali metals, alkaline earth metals, lanthanides, actinides, transition metals, and post transition metals.

A “metal ion” refers to an ion of a metal. Metal ions are generally Lewis Acids and can form coordination complexes. Typically, the metal ions used for forming a coordination complex in a framework are ions of transition metals.

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 “organic linking ligand” or “linking ligand” as used herein refers to an organic molecule that comprises a hydrocarbon and/or heterocycle parent chain that comprise at least two or more functional groups wherein these functional groups are used to form covalent bonds with other organic linking ligands. In the structure presented herein, these functional groups have been designated as LG (‘linking groups’) to distinguish these groups from other substitutions.

The term “substituted” with respect to hydrocarbons, heterocycles, and the like, refers to structures wherein hydrogen atoms have been replaced by a substituent.

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

The term “weaving agent” as used refers to an agent that can be used for bringing organic threads into a woven pattern so that the organic threads are mutually interlaced at regular or periodic intervals. In a particular embodiment, a “weaving agent” comprises metals, metal ions, or metal containing complexes that interact (e.g., form coordinate bonds) with two or more organic threads at certain geometries (e.g., tetrahedral, octahedral, paddle-wheel, etc.) so that the threads are assembled into a three-dimensional (3D) covalent organic framework. In a further embodiment, the organic threads have points-of-registry at the location of the weaving agents. While not being bound by any particular theory, the metal, metal ions, or metal containing complexes are postulated as seeking parts of the organic threads that are equally spaced from each other in order to bring together two organic threads in an up and down pattern like a weave. Examples of metals, metal ions that can be used as a weaving agent, 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⁺, R⁷⁺, 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⁺, Te⁶⁺, Te⁵⁺, 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⁺, La³⁺, La²⁺, and La⁺. Typically, the weaving agent is a tetrahedrally or octahedrally coordinating metal ion. In a particular embodiment, the weaving agent is Cu⁺.

Weaving, the mutual interlacing of long threads is one of the oldest and most enduring methods of making fabric, but this important design concept is yet to be emulated in extended chemical structures. Learning how to link molecular building units by strong bonds through reticular synthesis into weaving forms would be a boon to making materials with exceptional mechanical properties and dynamics. In order to successfully design weaving of chains into two- and three-dimensional (2D and 3D) chemical structures (see FIGS. 1A and B), long threads of covalently linked molecules should be able to cross at regular intervals. It would also be desirable if such crossings serve as points-of-registry so that the threads can have many degrees of freedom to move away and back to such points without collapsing the overall structure.

Provided herein is a general strategy and its implementation for the designed synthesis of a woven material (e.g., covalent organic framework-505, COF-505). For example, the disclosure teaches the synthesis of COF-505 which comprises helical organic threads interlacing to make a weaved crystal structure with the basic topology of FIG. 1B. It was further shown herein, that this woven material (e.g., COF-505) exhibited heretofore elasticity that was has not been previously seen in non-woven materials. Although terms such as interweaving, polycatenated and interpenetrating have been used to describe interlocking of 2D and 3D extended objects (see FIGS. 1C and D), most commonly found in MOFs, the “weaving” as used herein is used to describe exclusively the interlacing of units to make 2D and 3D structures (see FIGS. 1A and B). “Weaving” therefore differs from the commonly observed interpenetrating and polycatenated frameworks as the latter is topologically interlocking (i.e. interlocking rings, FIGS. 1C and D, insets). The woven constructs described herein have many more degrees of freedom than interweaving, polycatenated and interpenetrating materials. Thus, the woven constructs provided herein are capable of enormous spatial deviations by each of the threads that can take place independently and still preserve the underlying topology. Such freedom allows for reversible control over the mechanical properties of materials.

In a particular embodiment, the disclosure provides for a woven covalent organic framework (COF) that comprises a plurality of long organic helical threads that mutual interlace with each other together at regular or periodic intervals.

In a further embodiment, the disclosure provides for a long organic helical thread comprising linking ligands comprising the structure of Formula I:

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that are covalently linked with linking ligands comprising the structure of Formula II, III, or IV via a covalent bond formed between the LG groups of Formula I and the LG groups of Formula II, III, or IV:

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wherein,

R¹-R¹⁰, and R¹⁵-R⁴⁶are each independently selected from H, FG, (C₁-C₁₂)alkyl, substituted (C₁-C₁₂)alkyl, (C₂-C₁₂)alkenyl, substituted (C₂-C₁₂)alkenyl, (C₂-C₁₂)alkynyl, substituted (C₂-C₁₂)alkynyl, hetero-(C₁-C₁₂)alkyl, substituted hetero-(C₁-C₁₂)alkyl, hetero-(C₂-C₁₂)alkenyl, substituted hetero-(C₂-C₁₂)alkenyl, hetero-(C₂-C₁₂)alkynyl, substituted hetero-(C₂-C₁₂)alkynyl, (C₃-C₁₂)cycloalkyl, substituted (C₃-C₁₂)cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R⁵⁰)₃, —CH(R⁵⁰)₂, —CH₂R⁵⁰, —C(R⁵¹)₃, —CH(R⁵¹), —CH₂R⁵¹, —OC(R⁵⁰)₃, —OCH(R⁵⁰)₂, —OCH₂R⁵⁰, —OC(R⁵¹)₃, —OCH(R⁵¹), —OCH₂R⁵¹, or R¹-R¹⁰when adjacent can form a substituted or unsubstituted ring selected from the group comprising cycloalkyl, aryl and heterocycle;

R¹¹-R¹⁴are each independently selected from H, D, FG, (C₁-C₃)alkyl, substituted (C₁-C₃)alkyl, hetero-(C₁-C₃)alkyl, or substituted hetero-(C₁-C₃)alkyl.

R⁵⁰is selected from the group comprising FG, (C₁-C₁₂)alkyl, (C₁-C₁₂)substituted alkyl, (C₁-C₁₂)alkenyl, substituted (C₁-C₁₂)alkenyl, (C₁-C₁₂)alkynyl, substituted (C₁-C₁₂)alkynyl, hetero-(C₁-C₁₂)alkyl, substituted hetero-(C₁-C₁₂)alkyl, hetero-(C₁-C₁₂)alkenyl, substituted hetero-(C₁-C₁₂)alkenyl, hetero-(C₁-C₁₂)alkynyl, substituted hetero-(C₁-C₁₂)alkynyl;

R⁵¹is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle; and

n is an integer from 1 to 10. Examples of bonds that can result from reacting the FG groups of Formula I with the FG groups of Formula II, III, or IV include, but are not limited to:

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In yet a further embodiment, the disclosure provides for a long organic helical thread comprising linking ligands that have the structure of Formula I(a):

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that are covalently linked with linking ligands comprising the structure of Formula II(a), III(a), or IV(a):

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wherein,

R¹-R¹⁰, and R¹⁵-R⁴⁶are each independently selected from H, FG, (C₁-C₁₂)alkyl, substituted (C₁-C₁₂)alkyl, (C₂-C₁₂)alkenyl, substituted (C₂-C₁₂)alkenyl, (C₂-C₁₂)alkynyl, substituted (C₂-C₁₂)alkynyl, hetero-(C₁-C₁₂)alkyl, substituted hetero-(C₁-C₁₂)alkyl, hetero-(C₂-C₁₂)alkenyl, substituted hetero-(C₂-C₁₂)alkenyl, hetero-(C₂-C₁₂)alkynyl, substituted hetero-(C₂-C₁₂)alkynyl, (C₃-C₁₂)cycloalkyl, substituted (C₃-C₁₂)cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —OC(R⁵⁰)₃, —CH(R⁵⁰)₂, —CH₂R⁵⁰, —C(R⁵¹)₃, —CH(R⁵¹), —CH₂R⁵¹, —OC(R⁵⁰)₃, —OCH(R⁵⁰)₂, —OCH₂R⁵⁰, —OC(R⁵¹)₃, —OCH(R⁵¹), —OCH₂R⁵¹, or R¹-R¹⁰when adjacent can form a substituted or unsubstituted ring selected from the group comprising cycloalkyl, aryl and heterocycle;

R¹¹-R¹⁴are each independently selected from H, D, FG, (C₁-C₃)alkyl, substituted (C₁-C₃)alkyl, hetero-(C₁-C₃)alkyl, or substituted hetero-(C₁-C₃)alkyl.

R⁵¹is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle; and

LG is each independently selected from the group consisting of boronic acid, nitriles, aldehyde, amine, halide, hydroxyl, acyl halide, carboxylic acid, and acetic anhydride; and

n is an integer from 1 to 10. Examples of the foregoing,

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where m is an integer greater than 10, 20, 50 or 100.

In yet a further embodiment, the disclosure provides for a long organic helical thread that comprises linking ligands comprising the structure of Formula I(b):

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that are covalently linked with linking ligands comprising the structure of Formula II(b), III(b), or IV(b):

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wherein,

n is an integer from 1 to 10.

In a further embodiment, the disclosure provides for a woven covalent organic framework (COF) that comprises a plurality of long organic helical threads that mutual interlace with each other at regular intervals to form points-of registry, wherein the points-of-registry comprise the general structure of Formula V:

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wherein,

M is a metal ion, metal, or a metal complex that is bound to nitrogen atoms, or alternatively M is absent;

R¹-R¹⁰are each independently selected from H, FG, (C₁-C₁₂)alkyl, substituted (C₁-C₁₂)alkyl, (C₂-C₁₂)alkenyl, substituted (C₂-C₁₂)alkenyl, (C₂-C₁₂)alkynyl, substituted (C₂-C₁₂)alkynyl, hetero-(C₁-C₁₂)alkyl, substituted hetero-(C₁-C₁₂)alkyl, hetero-(C₂-C₁₂)alkenyl, substituted hetero-(C₂-C₁₂)alkenyl, hetero-(C₂-C₁₂)alkynyl, substituted hetero-(C₂-C₁₂)alkynyl, (C₃-C₁₂)cycloalkyl, substituted (C₃-C₁₂)cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R⁵⁰)₃, —CH(R⁵⁰)₂, —CH₂R⁵⁰, —C(R⁵¹)₃, —CH(R⁵¹), —CH₂R⁵¹, —OC(R⁵⁰)₃, —OCH(R⁵⁰)₂, —OCH₂R⁵⁰, —OC(R⁵¹)₃, —OCH(R⁵¹), —OCH₂R⁵¹, or R¹-R¹⁰when adjacent can form a substituted or unsubstituted ring selected from the group comprising cycloalkyl, aryl and heterocycle;

R¹¹-R¹⁴are each independently selected from H, D, FG, (C₁-C₃)alkyl, substituted (C₁-C₃)alkyl, hetero-(C₁-C₃)alkyl, or substituted hetero-(C₁-C₃)alkyl.

R⁵¹is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle; and

FG is selected from the group consisting of halos, hydroxyls, anhydrides, carbonyls, carboxyls, carbonates, carboxylates, aldehydes, haloformyls, esters, hydroperoxy, peroxy, ethers, orthoesters, carboxamides, amines, imines, imides, azides, azos, cyanates, isocyanates, nitrates, nitrites, 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)₃, Ge(SH)₃, AsO₃H, AsO₃H, P(SH)₃, As(SH)₃, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₃, Ge(SH)₃, Sn(SH)₃, AsO₃H, AsO₃H, P(SH)₃, and As(SH)₃. In a further embodiment, M is a metal, metal ion or metal complex comprising a metal or metal ion selected from the group consisting of 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⁺, La³⁺, La²⁺, and La⁺. In a particular embodiment, M is Cu⁺.

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wherein,

M is a tetrahedrally coordinating metal ion.

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Various structures presented herein can be synthesized using methods known in the art or are commercially available. In a particular embodiment, a compound having the structure of Formula I can be made by scheme I:

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Additional embodiments for synthesize a linking ligand disclosed herein are presented in FIG. 5.

By using the linking moieties described herein, extended chemical structures with mutual interlacing of long organic helical threads was emulated. In order to successfully design weaving of chains into two- and three-dimensional (2D and 3D) chemical structures (see FIGS. 1A and 1B), long organic helical threads were designed to cross at regular intervals. These crossings served as points-of-registry so that the threads can have many degrees of freedom to move away and back to such points without collapsing the overall structure.

The disclosure provides a general strategy and its implementation for the designed synthesis of a woven chemical material (e.g., covalent organic framework-505, COF-505). COF-505 has helical organic threads interlacing to make a weaving crystal structure with the basic topology of FIG. 1B, and show that this material has an unusual behavior in elasticity. Although terms such as interweaving, polycatenated and interpenetrating have been used to describe interlocking of 2D and 3D extended objects (see FIGS. 1C and D), most commonly found in MOFs, the term weaving is used herein to describe exclusively the interlacing of 1D units to make 2D and 3D structures (see FIGS. 1A and B). Weaving differs from the commonly observed interpenetrating and polycatenated frameworks as the latter is topologically interlocking (i.e. interlocking rings, FIGS. 1C and D, insets), while the weaving constructs provided here have many more degrees of freedom for enormous spatial deviations, by each of the threads, to take place independently and still preserve the underlying topology. Such freedom enables reversible control over the mechanical properties of materials.

The weaving strategy reported here is potentially applicable to the conversion of other network topologies to weaving structures. In addition to the dia net of COF-505, a variety of other two- and three-dimensional topologies can also be achieved by weaving of threads (variously colored) using metal ions as points-of-registry. Tetrahedrally coordinated metal complexes with two ligands can be employed as tetratopic building units in reticular synthesis to construct weaving structures of corresponding topologies (e.g. pnf, qtz and sod). Metal ions with an octahedral coordination geometry, which provides another type of points-of-registry by coordinating three ligands, can also be used to synthesize weaving structures (e.g. kgm and pcu).

The materials provided herein provide tunable mechanical properties and dynamics, and thus, can be used towards synthesis of resilient materials for a variety of purposes including shape-memory material development, biomedical applications, etc.

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

All starting materials and solvents, unless otherwise specified, were obtained from Aldrich Chemical Co. and used without further purification. Tetrahydrofuran (HPLC grade, Aldrich) was passed through a PureSolv MD 7 Solvent Purification System before use. 4,4′-(1,10-Phenanthroline-2,9-diyl)dibenzaldehyde was synthesized according to published literature. All reactions were performed at ambient laboratory conditions, and no precautions taken to exclude atmospheric moisture, unless otherwise specified. Pyrex glass tube charged with reagents and flash frozen with liquid N₂were evacuated using a Schlenk line by fitting the open end of the tube inside a short length of standard rubber hose that was further affixed to a ground glass tap which could be closed to insulate this assembly from dynamic vacuum when the desired internal pressure was reached. Tubes were sealed under the desired static vacuum using an oxygen propane torch.

Synthesis of 2,9-bis(4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)-1,10-phenanthroline (3; scheme I)

To a dry 500 mL round bottom flask, 2,9-dibromo-1,10-phenanthroline (1, 800 mg, 2.37 mmol), 2-(4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2, 1.69 g, 5.33 mmol), tetrakis(triphenylphosphine)palladium(0) (191 mg, 0.170 mmol) were added and stirred in 150 mL of toluene for 1 h at ambient temperature under nitrogen. Subsequently, barium hydroxide (2.24 g, 7.10 mmol) and 150 mL of water was added. This mixture was heated at reflux overnight, after which the reaction was cooled to ambient temperature. The layers were separated and the aqueous layer was washed with dichloromethane (DCM, 50 mL×3). The organic layers were combined and dried over MgSO₄. The solvent was removed by evaporation in vacuo and the resulting crude product was purified using column chromatography was with DCM. Product 3 was isolated as a white solid (923 mg, 70% yield). 1H NMR (400 MHz, Chloroform-d) δ 8.49 (d, J=8.3 Hz, 4H), 8.29 (d, J=8.4 Hz, 2H), 8.15 (d, J=8.4 Hz, 2H), 7.78 (s, 2H), 7.73 (d, J=8.3 Hz, 4H), 5.52 (s, 2H), 3.84 (d, J=11.0 Hz, 4H), 3.72 (d, J=11.0 Hz, 4H), 1.36 (s, 6H), 0.84 (s, 6H).

Synthesis of 4,4′-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde (4; Scheme I)

A 5% HCl aqueous solution (36 mL) was added to a stirring solution of 3 (900 mg, 1.61 mmol) in tetrahydrofuran (180 mL). The mixture was stirred at ambient temperature for 48 h, and then the solvent was evaporated in vacuo. The residue was suspended in a saturated NaHCO₃aqueous solution (100 mL) and DCM (100 mL). The organic layer was collected and dried over MgSO₄. The solvent was removed by evaporation and resulting crude product was purified by column chromatography using DCM. Product 4 was isolated as a white solid (525 mg, 84% yield). 1H NMR (400 MHz, Chloroform-d) δ 10.15 (s, 2H), 8.63 (d, J=8.2 Hz, 4H), 8.40 (d, J=8.4 Hz, 2H), 8.23 (d, J=8.4 Hz, 2H), 8.12 (d, J=8.2 Hz, 4H), 7.88 (s, 2H).

Synthesis of Cu(PDB)₂complex (5; Scheme I)

A degassed solution of Cu(CH₃CN)₄BF₄(211 mg, 0.670 mmol) in CH₃CN (12.5 mL) was added to a degassed solution of 4 (521 mg, 1.34 mmol) in CHCl₃(25 mL). The solution immediately turned red, indicating complex formation. After the solution was stirred at ambient temperature for 0.5 h, the solvent was removed by evaporation in vacuo. Product 5 was isolated as a red solid (620 mg, quantitative yield). 1H NMR (400 MHz, DMSO-d6) δ 9.67 (s, 4H), 8.82 (d, J=8.3 Hz, 4H), 8.18 (d, J=8.3 Hz, 4H), 8.14 (s, 3H), 7.61 (d, J=7.8 Hz, 8H), 7.07 (d, J=7.8 Hz, 8H). Solution ¹H nuclear magnetic resonance (NMR) spectra were recorded on a Bruker AVQ-400 (400 MHz) spectrometer operating with an Avance electronics console.

Synthesis of COF-505

Synthesis of Cu(I)-bis[4,4′-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde] tetrafluoroborate [Cu(PBD)₂]: [Cu(CH₃CN)₄]BF₄(388 mg, 1.00 mmol) was dissolved in anhydrous CH₃CN (8 mL) under a N₂atmosphere and then added to a solution of 4,4′-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde (157 mg, 0.500 mmol) in CHCl₃(16 mL), affording a dark red solution. After stirring the solution at ambient temperature for 30 min, the solution was then concentrated in vacuo to afford an analytically pure compound as a red solid (545 mg, quantitative). ¹H NMR (400 MHz, CDCl₃) δ 9.69 (s, 4H), 8.29 (d, 3J=7.9 Hz, 8H), 8.18 (d, 3J=8.4 Hz, 4H), 8.07 (d, 3J=8.4 Hz, 4H), 7.70 (d, 3J=7.9 Hz, 8H), 7.60 (s, 4H). ESI-MS for [C₅₂H₃₂CuN₄O₄]⁺ (Calcd. 839.17): m/z=839.17 ([M]⁺, 100%); Elemental analysis: Calcd. For C₁₀₀H₆₈BCuF₄N₈: C, 67.36; H, 3.48; N, 6.04%. Found: C, 66.34; H, 3.37; N, 5.81%.

Synthesis and Activation of COF-505

A Pyrex tube measuring 10×8 mm (o.d×i.d) was charged with Cu(PBD)₂(15 mg, 0.016 mmol), benzidine (6.0 mg, 0.032 mmol), anhydrous THF (1 mL) and 6 M aqueous acetic acid solution (0.1 mL). The tube was flash frozen at 77 K (liquid N₂bath), evacuated to an internal pressure of 50 mTorr and flame sealed. Upon sealing, the length of the tube was reduced to 18-20 cm. The reaction was heated at 120° C. for 72 h yielding a brown solid at the bottom of the tube which was isolated by centrifugation and washed with anhydrous THF and dried at 120° C. under 50 mTorr for 12 h. This material is insoluble in water and common organic solvents such as hexanes, methanol, acetone, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide, indicating the formation of an extended structure. Yield: 18.7 mg, 94.4% based on Cu(PBD)₂. Elemental analysis: for C₇₆H₄₈BCuF₄N₈.4H₂O: Calcd. C, 70.45; H, 4.36; N, 8.65%. Found: C, 70.13; H, 4.03; N, 8.50%.

Synthesis of the molecular analogue of COF-505, Cu(I)-bis[(1E,1′E)-1,1′-((1,10-phenanthroline-2,9-diyl)bis(4,1-phenylene))bis(N-([1,1′-biphenyl]-4-yl)methanimine)] tetrafluoroborate [Cu(PBM)₂]

A mixture of Cu(PBD)₂(50.0 mg, 0.108 mmol) and 4-phenyl-aniline (110 mg, 0.648 mmol) in anhydrous p-xylene and CHCl₃1:1 mixture (15 mL) was stirred under reflux equipped with a Dean-Stark apparatus over 24 h. A dark grey solid was precipitated by adding additional p-xylene after cooling down the mixture to ambient temperature. The precipitant was collected by filtration and dried in vacuo(49 mg, 99% yield). 1H NMR (600 MHz, DMSO-d6) δ 8.81 (d, 3J=8.1 Hz, 4H), 8.33 (s, 4H), 8.19 (d, 3J=8.2 Hz, 4H), 8.12 (s, 4H), 7.76 (d, 3J=7.8 Hz, 8H), 7.72 (d, 3J=7.5 Hz, 8H), 7.60 (d, 3J=7.9 Hz, 8H), 7.49 (t, 3J=7.7 Hz, 8H), 7.39 (s, 4H), 7.37 (d, 3J=7.5 Hz, 8H), 7.13 (d, 3J=7.7 Hz, 8H). ESI-MS for [C₁₀₀H₆₈CuN₈]⁺ (Calcd. 1444.49): m/z=1444.48 ([M]+, 100%); Elemental analysis: Calcd. For C₁₀₀H₆₈BCuF₄N₈: C, 78.40; H, 4.47; N, 7.31%. Found: C, 76.25; H, 4.55; N, 6.92%.

Single-Crystal X-Ray Diffraction.

Single-crystals of the complex were crystallized by the slow diffusion of hexane vapor into a CH₂Cl₂solution of Cu(PBD)₂. A red block-shaped crystal (0.150×0.120×0.100 mm) was mounted on a Bruker D8 Venture diffractometer equipped with a fine-focus Mo target X-ray tube operated at 40 W power (40 kV, 1 mA) and a PHOTON 100 CMOS detector. The specimen was cooled to −123° C. using an Oxford Cryosystem chilled by liquid nitrogen. The Bruker APEX2 software package was used for data collection; the SAINT software package was used for data reduction; SADABS was used for absorption correction; no correction was made for extinction or decay. The structure was solved by direct methods in a triclinic space group P-1 with the SHELXTL software package and further refined with the least squares method. All non-hydrogen atoms were refined anisotropically, all hydrogens were generated geometrically. The details of crystallography data are shown in TABLE 1 and TABLE 2.

TABLE 1

Crystal data and structure refinement Cu(PBD)₂.

Chemical formula
C₅₃H₃₄BCl₂CuF₄N₄O₄

Formula weight
1012.09

Wavelength
0.71073 Å

Crystal system
Triclinic

Space group
P-1

Unit cell dimensions
a = 12.987(5) Å
α = 88.288(7)°

b = 12.995(5) Å
β = 81.131(7)°

c = 14.074(5) Å
γ = 67.000(6)°

Volume
2159.1(13) Å³

Z
2

Absorption coefficient
0.703 mm⁻¹

Crystal size
0.150 × 0.120 × 0.100 mm³

Theta Min-Max
1.465 to 25.427°

Reflections collected
73691

Independent reflections
7942 [R(int) = 0.0510]

Completeness to theta =
100.0%

25.000°

Goodness-of-fit on F²
1.046

Final R indices [I > 2σ(I)]
R₁= 0.0358, wR₂= 0.0961

R indices (all data)
R₁= 0.0399, wR₂= 0.0999

Largest diff. peak and hole
0.782 and −0.485 e · Å⁻³

The geometry around the copper can be described as distorted tetrahedral with approximate C₂symmetry. The C₂symmetry is indicated by the six N—Cu—N bond angles and the four Cu—N bonds in similar lengths (TABLE 2).

TABLE 2

Selected Structural Data for Complex Cu(PBD)₂.

Distances/Å

N(1)—Cu(1)
2.0624(18)

N(2)—Cu(1)
2.0626(18)

N(3)—Cu(1)
2.1011(18)

N(4)—Cu(1)
2.0349(18)

Angles/°

N(4)—Cu(1)—N(1)
142.26(7)

N(4)—Cu(1)—N(2)
126.80(7)

N(1)—Cu(1)—N(2)
82.22(7)

N(4)—Cu(1)—N(3)
81.55(7)

N(1)—Cu(1)—N(3)
123.16(7)

N(2)—Cu(1)—N(3)
95.82(7)

The C₂axis bisects the N1B—Cu—N1A angle, thus relating the two phenanthroline ligands and resulting in approximate molecular C₂symmetry. A significant feature of the structure is the n-stacking interactions at 3.4 Å and 3.8 Å between phenanthrolines A and B and phenyl groups E and C, respectively (see FIG. 6). In addition, intermolecular phenyl-phenyl n-stacking interactions at 4.0 Å are also present, resulting in phenyl-phenanthroline-phenyl-phenyl-phenanthroline-phenyl n-stacks in the unit cell.

Fourier Transform Infrared Spectroscopy.

The FT-IR spectra of starting materials, molecular analogue, and activated COFs were collected on a Bruker ALPHA FT-IR Spectrometer equipped with ALPHA's Platinum ATR single reflection diamond ATR module, which can collect IR spectra on neat samples. The signals are given in wavenumbers (cm⁻¹) and described as: very strong (vs), strong (s), medium (m), shoulder (sh), weak (w), very weak (vw) or broad (br) (see TABLE 3).

TABLE 3

Peak assignment for the FT-IR spectrum of COF-505. Notes

and discussion are provided to correlate the spectra of starting

material.

Peak (cm⁻¹)
Assignment and Notes

3029 (vw)
Aromatic C—H stretch from phenyl rings in

complex Cu(PBD)₂. Present in model compound

Cu(PBM)₂.

2868 (vw)
Alkene C—H stretching from imine. Present in

Cu(PBM)₂.

1621 (m)
Imine C═N stretching. Present in Cu(PBM)₂. This

bond is confirmed by the disappearance of the

ν_N—Hstretching mode from tetraanilylmethane

(3319 cm⁻¹) and of the ν_C═Ostretching mode from

biphenyldicarboxaldehyde (1693 cm⁻¹).

1595 (m)
Aromatic C═C ring stretching from benzidine.

1581 (m)
Aromatic C═C ring stretching from phenyl rings

in complex Cu(PBD)₂.

1564 (m)
Aromatic C═C ring stretching from Cu(PBD)₂.

1515 (m)
Aromatic C═C ring stretching from Cu(PBD)₂.

1489 (s)
Aromatic C—C ring stretching from Cu(PBD)₂.

1413 (w)
Aromatic C—C ring stretching from Cu(PBD)₂.

1356 (m)
Aromatic C—C ring stretching from Cu(PBD)₂.

1299 (w)
Aromatic ring stretching from Cu(PBD)₂.

1281 (w)
Aromatic ring stretching from Cu(PBD)₂.

1196 (m)
Imine C—C═N—C stretching. This mode is the

stretching of the C—C and C—N single bonds.

1171 (m)
C—Ph breathing and C—C stretching from

benzidine, characteristic of biphenyl.

1056 (w)
B—F stretching from BF₄anions.

1013 (sh)
Aromatic C—H in-plane bending from phenyl rings

in Cu(PBD)₂.

1003 (sh)
Aromatic C—H in-plane bending from phenyl rings

in Cu(PBD)₂.

976 (sh)
Aromatic C—H in-plane bending from phenyl rings

in Cu(PBD)₂.

886 (m)
Aromatic C—H phenyl ring substitution bands

from biphenyl rings in benzidine.

834 (s)
Aromatic ring stretching from Cu(PBD)₂.

795 (m)
Aromatic ring stretching from Cu(PBD)₂.

748 (m)
Aromatic ring C—H out-of-plane bending from

Cu(PBD)₂.

727 (m)
Aromatic ring C—H out-of-plane bending from

Cu(PBD)₂.

690 (w)
Aromatic ring C—H out-of-plane bending from

Cu(PBD)₂.

649 (w)
Aromatic ring C—H out-of-plane bending from

Cu(PBD)₂.

557 (m)
Aromatic ring C—H out-of-plane bending from

Cu(PBD)₂.

540 (m)
Aromatic ring C—H out-of-plane bending from BZ.

520 (m)
Aromatic ring C—H out-of-plane bending from

Cu(PBD)₂.

477 (w)
Aromatic ring C—H out-of-plane bending from BZ.

Solid-State Nuclear Magnetic Resonance Spectroscopy.

Solid-state nuclear magnetic resonance (NMR) spectra were recorded at ambient pressure on a Bruker AV-500 spectrometer using a standard Bruker magic angle-spinning (MAS) probe with 4 mm (o.d.) zirconia rotors. The magic angle was adjusted by maximizing the number and amplitudes of the signals of the rotational echoes observed in the ⁷⁹Br MAS FID signal from KBr. The transmitter frequency of ¹³C NMR is 125.80 MHz.

The solid-state ¹³C NMR spectra were acquired using cross-polarization (CP) MAS technique with the ninety degree pulse of ¹H with 4.2 μs pulse width. The CP contact time was 2 ms. High power two-pulse phase modulation (TPPM)¹H decoupling was applied during data acquisition. The decoupling frequency corresponded to 32 kHz. The MAS sample spinning rates was 11 kHz. Recycle delays between scans were 2 s. The ¹³C chemical shifts are given relative to neat tetramethylsilane as zero ppm, calibrated using the methylene carbon signal of adamantane assigned to 38.48 ppm as secondary reference.

The experimental setup for cross-polarization and polarization inversion (CPPI) spectral editing is the same as the CPMAS experiment. Pulse sequences are included in work by Zilm and co-workers. Spectral editing parameters were determined as ¹H with 6 μs pulse width, cross-polarization times of 2 ms, and a polarization inversion time of 40 μs.

Scanning Electron Microscopy.

Samples of COF-505 for SEM study were prepared by drop casting the acetone dispersion of the material onto a 1 cm²silicon wafer. SEM images were recorded on a Zeiss Gemini Ultra-55 Analytical scanning electron microscope with accelerating voltage of 5 kV with a working distance of 5 mm. Primary crystallites of size of 0.2×0.2 μm were aggregated into spheres with diameter of approximately 2 μm. No other forms were observed in the surveyed samples, and from morphology of primary crystallites were in the same phase.

Electron Diffraction Analyses by Transmission Electron Microscopy.

A cold field emission JEM-2100F equipped with a DELTA C_scorrector operated at 60 kV was used for HRTEM imaging. Since COF materials are electron beam sensitive, the electron beam damage to the specimen was minimized as much as possible (in this study, the beam density during the observations was less than 500 electrons/(nm²·s)). A Gatan 894 CCD camera was used for digital recording of the HRTEM images. A single HRTEM image with an exposure time of 2 seconds or a sequence of images (up to 20 frames) was recorded, with a 1 or 2 seconds exposure time for each. After drift compensation, some frames can be superimposed to increase the signal-to-noise (SN) ratio for display. HRTEM images are filtered by a commercial software named HREM-Filters Pro (HREM Research Inc. Japan).

COF-505 crystals were dispersed into ethanol by ultrasonic oscillation and then dropped on a carbon film supported TEM grid. 3D electron diffraction tomography (3D-EDT) data were collected on a JEOL JEM-2100, with LaB6 filament and the control of EDT-collect program. The data was further processed by EDT-process program (see TABLE 4).

TABLE 4

Plane group of projection along [1-10] and multiplicities

of general site for five different space groups

Space group
Cm2a
Cmma
Cmca
Cc2a
Ccca

Plane group projected
pg
pg
pgg
pgg
pmg

along [1-10]

Multiplicity for
8
16
16
8
16

general site

Powder X-Ray Diffraction Analysis.

Powder X-ray diffraction data of complex A and benzidine B were collected using a Bruker D8-advance θ-θ diffractometer in parallel beam geometry employing Cu Kα1 line focused radiation at 1600 W (40 kV, 40 mA) power and equipped with a position sensitive detector with at 6.0 mm radiation entrance slit. Samples were mounted on zero background sample holders by dropping powders from a wide-blade spatula and then leveling the sample with a razor blade. The best counting statistics were achieved by collecting samples using a 0.02° 2θ step scan from 1-40° with exposure time of 5 s per step.

PXRD of COF-505 was obtained by wide angle X-ray scattering (WAXS) using Pilatus 2M (Dectris) instrument on beamline 7.3.3 at the Advanced Light Source, Lawrence Berkeley National Laboratory (λ=1.24 Å). The sample-detector distance and beam center were calibrated using silver behenate. 1-D scattering profiles were reduced from the 2-d data using the Nika package for IGOR Pro (Wavemetrics). The 1-D plot shown in this material are plotted from WAXS data converted to 26 values assuming λ=1.5406 Å (Cu Kα1).

Structural Modeling:

Unit cell parameters and possible space groups were determined using the electron diffraction experiments. The unit cell parameters were refined against the PXRD pattern with a Pawley refinement (a=18.6419 Å, b=21.4075 Å, c=30.2379 Å, orthorhombic, space group Cc2a). The initial positions of copper ions were obtained at the maxima of reconstructed 3D potential map from Fourier analysis of HRTEM image. A crystal model was built accordingly with the use of Materials Studio v6.0. Eight complex Cu(PDB)₂molecules were put into one unit cell as a rigid body with copper positions fixed. The orientation of complex was initially refined using PXRD pattern. To make it an extended structure and according to the spectroscopic characterization, one Cu(PDB)₂was connected to its four neighbors through BZ molecules. Then the crystal structure was optimized through a combination of energy and geometrical minimization and PXRD Rietveld refinement. Anions BF₄⁻ were finally introduced into the model to compensate the charge of the Cu complexes, and to account for the missing electron density from electron diffraction studies. Since the position of the BF₄⁻ anions does not affect the overall framework, the accurate positions of the anions may vary. The structure was further refined with the Rietvled method (Rwp=6.23%, Rp=4.35%).

The chemical content in one unit cell is B₈C₆₀₈Cu₈F₃₂H₃₈₄N₆₄, consisting of eight symmetrically equivalent Cu(PBD)₂, BZ and BF₄units. The geometry of Cu(PBD)₂in COF-505 was similar to that in its molecular crystal. The building units Cu(PBD)₂are connected to each other through imine bonds with biphenyl linkers BZ. The closest distance between two Cu atoms is 8.5 Å. This short distance does not allow the connection between these two Cu(PBD)₂and two mutually weaving nets are formed. The continuous connection of PDB and BZ units formed a helical thread along [110] or [−110] directions. As a result, COF-505 is a weaved framework consisting of helical threads.

The two frameworks are mutually woven in a way that is different to the commonly observed interpenetration and polycatenation modes. In the normally observed 2-fold dia interpenetration every 6-ring of one network is crossed by one and only one edge of the other network. However, some 6-rings are crossed by three edges of the other network and some edges pass through more than one rings in COF-505 network. This mode of polycatenation and interpenetration makes the particular weaving pattern in the structure COF-505.

There is a minor phase found in HRTEM observations, which displays the same plane group symmetry as COF-505 along [1-10], but with slightly different lattice constants (see FIG. 15). The structure cannot be solved without whole 3d diffraction data, however this image can be explained if this nano-crystal has the same structure as the COF-505 with slight changes in lattice constants (d₁₁₀/d₀₀₁=12/31), i.e. contraction along [110] direction (d₁₁₀=12 Å compared to 14.2 Å for COF-505 if lattice constant c is kept constant) and/or expansion of lattice parameter c.

Thermalgravimetric Analysis.

Samples were run on a TA Instruments Q-500 series thermal gravimetric analyzer with samples held in a platinum pan under nitrogen atmosphere. A ramp rate of 5° C./min was used.

Synthetic Procedure for De-Metalation and Re-Metalation.

A 0.3 M KCN solution in a 1:5 mixture of MeOH and H₂O was added to a suspension of COF-505 powder. The solution was heated at 90° C. The solution was replaced by a fresh solution of KCN every 24 h and this procedure was repeated three times. Control experiments without KCN solution was also conducted under otherwise identical conditions. Subsequently, both samples were washed with anhydrous CH₃OH and dried at 120° C. under 50 mTorr for 12 h. The de-metalated material was observed to be pale-yellow in color, in contrast to the dark brown color of COF-505 (see FIG. 19).

The re-metalation process was carried out in similar conditions with the complexation reaction to yield complex Cu(PBD)₂. Dried powder of the de-metalated material was immersed in anhydrous CHCl₃, to which was added a 0.01 M Cu(CH₃CN)BF₄solution in CH₃CN. This mixture was stirred for 12 h under N₂at ambient temperature and dark brown color was recovered (see FIG. 19).

Inductively Coupled Plasma Atomic Emission Spectroscopy.

Inductively coupled plasma atomic emission spectroscopy (ICP-AES) was used to determine the copper content in these materials. Samples were dissolved in OPTIMA grade nitric acid. The stock solutions were then diluted to 1:10 (v/v) with H₂O, which were analyzed on an Agilent 7500ce ICP-AES using helium collision gas mode. The copper content in COF-505 (C₇₆H₄₈BCuF₄N₈.4H₂O) is calculated to be 4.9% and measured to be 4.8%, while in the de-metalated material, it was determined to be in the range of 0.15% to 0.38%, approximately 3-8% of the original Cu concentration. After re-metalation, the Cu content was determined to be 3.9% to 4.2%, which is 82-88% of COF-505.

Atomic Force Microscopy.

Nano-indentation based on AFM (Nanoscope Dimension 3100) was employed to measure Young's modulus of COF-505 and the de-metalated material. AFM images of the particles were first acquired under non-contact mode (see FIGS. 25A and B), followed by indentation at the summit of the aggregate which is relatively flat.

Following the standard procedure of nano-indentation, the Young's modulus is related to the indentation curve by Eq. (1):

$\begin{matrix} S = \frac{dP}{dh} = β \frac{2}{π} E_{eff} \sqrt{A} & (1) \end{matrix}$

Where

$\frac{1}{E_{eff}} = \frac{1 - v^{2}}{E} + \frac{1 - v_{i}^{2}}{E_{i}}$

is the effective elastic modulus of the system, E_eff, reflecting both the mechanical response of the sample, E, and the indenter, E_i, and ν is Poisson's ratio.

Synthesis and Characterization of COF-505

A synthetic strategy to produce COF-505 is presented in FIG. 2, where an aldehyde functionalized derivative is used to exemplify the well-known complex salt Cu(I)-bis[4,4′-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde] tetrafluoroborate, Cu(PDB)₂(BF₄) (see FIG. 2A). The position of the aldehyde groups approximates a tetrahedral geometry which can be used in reticular synthesis as a building block to be linked with benzidine (BZ) to generate imine-bonded PDB-BZ threads in a woven arrangement with the tetrafluoroborate anions occupying the pores (see FIG. 2B). The orientation of the PDB units in a mutually interlacing fashion ensures that the threads produced from linking of the building units are entirely independent, with the Cu(I) ions serving as templates (points-of-registry) to bring those threads together in a precise manner at well-defined intervals. Because the PDB-BZ threads are topologically independent of the Cu(I) ions, the resulting woven structure is formally a COF (termed COF-505). The overall tetrahedral geometry of the aldehyde units ensures the assembly of the threads into a 3D framework (see FIG. 2B). The topology of this framework is that of diamond as expected from the principles of reticular chemistry. In addition, even after the removal of the Cu(I) ions, the structure and its topology remain intact irrespective of how the threads deviate from their points-of-registry, and upon re-metalating the overall structure is reversibly restored. A ten-fold increase in elasticity was found when going from the metalated to the de-metalated forms of the material.

The copper(I)-bisphenanthroline core of the Cu(PDB)₂(without the aldehyde functionality) has been studied extensively as a discrete molecule for the formation of supramolecular complexes; however, as yet, it has not been used to make extended structures especially of the type discussed here. The tolerance for robust reaction conditions makes this complex suitable for imine COF synthesis, especially in weak acidic conditions. Thus, the tetrahedral building unit, Cu(PDB)₂, was designed bearing aldehyde groups in the para positions of the two phenyl substituents (see FIG. 2A). The synthesis of Cu(PDB)₂(BF₄) molecular complex was carried out by air-free Cu(I) complexation of 4,4′-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde according to a previously reported procedure. The single-crystal structure of this complex revealed a distorted tetrahedral geometry around the Cu(I) center, with a dihedral angle of 57° between the two phenanthroline planes. This distortion likely arises from the n-n interaction between the phenanthroline and neighboring phenyl planes.

COF-505 was synthesized via imine condensation reactions by combining a mixture of Cu(PDB)₂(BF₄) (15 mg, 0.016 mmol) and BZ (6.0 mg, 0.032 mmol) in tetrahydrofuran (THF, 1 mL) and aqueous acetic acid (6 mol/L, 100 μL). The reaction mixture was sealed in a Pyrex tube and heated at 120° C. for 3 days. The resulting precipitate was collected by centrifugation, washed with anhydrous THF, and then evacuated at 120° C. for 12 h to yield 18.7 mg [94.4% based on Cu(PDB)₂(BF₄)] of a dark brown crystalline solid (COF-505), which was insoluble in common polar and nonpolar organic solvents.

Fourier-transform infrared spectroscopy (FT-IR) and solid-state nuclear magnetic resonance (NMR) spectroscopy studies were performed on COF-505 to confirm the formation of imine linkages. A molecular analog of COF-505 fragment, Cu(I)-bis[(1,10-phenanthroline-2,9-diyl)bis(phenylene)bis(biphenyl)methanimine)] tetrafluoroborate, Cu(PBM)₂(BF₄), was used as a model compound and synthesized by condensation of Cu(PDB)₂(BF₄) and 4-aminobiphenyl. The FT-IR spectrum of COF-505 shows peaks at 1621 and 1196 cm⁻¹[1622 and 1197 cm⁻¹for Cu(PBM)₂(BF₄)], which are characteristic C═N stretching modes for imine bonds. Furthermore, the ¹³C cross-polarization with magic-angle spinning (CPMAS) solid-state NMR spectrum acquired for COF-505 displays a series of peaks from 140 to 160 ppm, similar in shape and occurring at chemical shifts characteristic of those expected for C═N double bonds. In order to differentiate imine bonds from C═N double bonds of the phenanthroline unit, a cross-polarization and polarization inversion (CPPI) technique was applied, which leaves the signal for quaternary ¹³C groups unchanged, while the residual tertiary ¹³CH signal should approach zero. The decreased intensity of the ¹³CH signal under these conditions confirmed the existence of imine CH═N double bond. Overall, these observations served as initial confirmation of having covalently linked imine extended threads in COF-505.

Prior to determining the single crystal structure of COF-505, the morphology and purity of the as-synthesized material was analyzed. Using scanning electron microscopy (SEM), crystallites of ˜200 nm are aggregated into spheres of 2 μm in diameter (see FIG. 3A), which possibly arises from weak interactions of the synthesized material with the solvent, THF. No other phase was observed from SEM images taken throughout the material.

A single submicrometer-sized crystal (see FIG. 3B) from this sample was studied by 3D electron diffraction tomography (3D-EDT). One EDT data set was collected from the COF-505 (see FIG. 3C) by combining specimen tilt and electron-beam tilt in the range of −41.3° to +69.1° with a beam-tilt step of 0.2°. From the acquired data set, 3D reciprocal lattice of COF-505 was constructed that was identified as a C-centered orthorhombic Bravais lattice. The unit cell parameters were a=18.9 Å, b=21.3 Å, c=30.8 Å and V=12399 Å³, which were used to index reflections observed in both powder x-ray diffraction (PXRD) pattern and Fourier diffractograms of high-resolution TEM images (see FIG. 3D to F). The unit cell parameters were further refined to be a=18.6 Å, b=21.4 Å, c=30.2 Å, V=12021 Å³by Pawley refinement of PXRD pattern (see FIG. 3G). The observed reflection conditions were summarized as hk1: h+k=2n; hk0: h,k=2n; h01: h=2n; 0k1: k=2n, suggesting five possible space groups, Cm2a (No. 39), Cmma (No. 67), Cmca (No. 64), Cc2a (No. 41) and Ccca (No. 68). Three of them, Cm2a, Cmma, and Ccca, were excluded, as their projected symmetries along [1-10] did not coincide with that of HRTEM image, pgg (see FIG. 3E). Furthermore, by performing Fourier analysis of the HRTEM images and imposing symmetry to the reflections, Cu(I) positions were determined from the reconstructed 3D potential map (see FIG. 3F). The structure of COF-505 was built in Materials Studio by putting Cu(PDB)₂units at copper positions and connecting them through biphenyl (reacted BZ) molecules. The chemical compositions were determined by elemental analysis, therefore once the number of copper atoms in one unit cell was obtained, the numbers of other elements in one unit cell were also determined, which indicates that the unit-cell framework is constructed by 8 Cu(PDB)₂and 16 biphenyl units. However, symmetry operations of the space group Cmca requires two PDB units connected to one copper onto a mirror plane perpendicular to a axis, which is not energetically favorable geometry. The final space group determined, Cc2a, was used to build and optimize a structure model. The PXRD pattern calculated from this model is consistent with the experimental pattern of activated COF-505.

According to the refined model, COF-505 crystallizes in a diamond (dia) network with the distorted tetrahedral building units Cu(PBD)₂and biphenyl linkers BZ linked through trans imine bonds. As a result, covalently linked adamantane-like cages 19 Å by 21 Å by 64 Å are obtained and elongated along the c-axis (dimensions are calculated based on Cu-to-Cu distances). This size allows two diamond networks of identical frameworks to form the crystal. These frameworks are mutually interpenetrating (when the Cu centers are considered) in COF-505 crystals along the c direction, where the frameworks are related by a C₂rotation along the b-axis, leaving sufficient space for BF₄⁻ counter-ions. When the structure is de-metalated, as demonstrated below, the COF is mutually woven (see FIG. 2B).

Fundamentally, each of the threads making up the framework is a helix (see FIG. 4A). For clarity, only a fragment of one weaving framework is shown. The helices are entirely made of covalently linked organic threads. As expected, they are weaving and being held by Cu(I) ions at their points-of-registry (see FIG. 4B). These threads are propagating in two different directions along [110] and [−110]. Although the helices are chemically identical, they have opposite chirality giving rise to an overall racemic weaving framework (see FIGS. 4C and D) of the same topology as in FIG. 1B. It was noted that in the context of reticular chemistry, the points-of-registry play an important role in crystallizing otherwise difficult to crystallize threads and to do so into two- or three-dimensional frameworks. This arrangement is in stark contrast to the parallel manner in which such one-dimensional objects commonly pack in the solid-state.

The exemplary COF-505 structure is a woven fabric of helices. Experiments were performed to remove the Cu centers and examine the properties of the material before and after de-metalation. Heating COF-505 in a KCN methanol-water solution yielded a de-metalated material. Using inductively coupled plasma (ICP) analysis, 92-97% of the Cu(I) copper ions had been removed. The dark brown color of COF-505 [from the copper-phenanthroline metal-to-ligand charge transfer (MLCT)] changed to pale-yellow as de-metalation proceeded. Although the crystallinity of de-metalated material decreased compared to COF-505, SEM images show similar morphology before and after de-metalation. Additionally, the imine linkages were also maintained; the FT-IR peaks at 1621 and 1195 cm⁻¹are consistent with those of COF-505 (1621 and 1196 cm⁻¹). Furthermore, the material could be re-metalated with Cu(I) ions by stirring in a CH₃CN/CH₃OH solution of Cu(CH₃CN)₄(BF₄) to give back crystalline COF-505. This re-metalated COF-505 has identical crystallinity to the original as-synthesized COF-505 as evidenced by the full retention of the intensity and positions of the peaks in the PXRD. In the FT-IR spectrum, the peak representing imine C═N stretch was retained, indicating that the framework is chemically stable and robust under such reaction conditions.

Given the facileness with which de-metalation can be carried out and the full retention of the structure upon re-metalation can be achieved, the elastic behavior of the metalated and de-metalated COF-505 was examined. A single particle of each of these two samples was indented by a conical tip of an atomic force microscope and the load-displacement curves were recorded for both loading and unloading process. The effective Young's moduli (neglecting the anisotropy of the elasticity) of the two COF-505 materials was ˜12.5 GPa and 1.3 GPa for the metalated and de-metalated particles, respectively. Remarkably, this ten-fold ratio in elasticity upon de-metalation of COF-505 is similar to the elasticity ratio for porous MOFs to polyethylene. The distinct increase of elasticity could be attributed to the loose interaction between the threads upon removal of copper. Moreover, the elasticity of the original COF-505 could be fully recovered after the process of de-metalation and re-metalation, being facilitated by the structure of weaving helical threads that easily ‘zip’ and ‘unzip’ at their points-of-registry. The large difference in elasticity modulus is caused by loss of Cu(I) ions, which in total only represent a minute mole percentage (0.67 mol %) of the COF-505 structure.

For COF-505, it was found that the indentation curve is close to pure elastic deformation at small depth described by the Hertz theory (see FIG. 25C). Its Young's modulus is calculated to be 12.5 GPa using a tip radius of 15 nm, and Poisson's ratio of ν=0.3. This value lies within the typical range of MOFs. The measured Young's moduli of other COF-505 particles and re-metalated COF-505 are within 30% deviation. On the contrary, the de-metalated material is very soft and shows significant plastic deformation under moderate force (see FIGS. 25C and D). Applying Eq. (1) a Young's modulus around 1.3 GPa was obtained when assuming a tip radius of 15 nm and a tip angle of 30°.

The weaving strategy reported here is potentially applicable to the conversion of other network topologies to weaving structures as illustrated in FIG. 26. In addition to the dia net of COF-505, a variety of other two- and three-dimensional topologies can also be achieved by weaving of threads (variously colored) using metal ions as points-of-registry. Tetrahedrally coordinated metal complexes with two ligands can be employed as tetratopic building units in reticular synthesis to construct weaving structures of corresponding topologies (e.g., pnf, qtz and sod). Metal ions with an octahedral coordination geometry, which provides another type of points-of-registry by coordinating three ligands, can also be used to synthesize weaving structures (e.g., kgm and pcu).

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 woven covalent organic framework that comprises a plurality of long organic threads that are mutually interlaced at regular intervals so as to form points-of-registry, wherein the points-of-registry have a structure represented by Formula V:
2. The woven covalent organic framework of claim 1, wherein the covalent bond formed between the LG groups of Formula I and the LG groups of Formula II, III, or IV, has the structure of:
3. The woven covalent organic framework of claim 1, wherein the alternating linking ligands comprise linking ligands that have a structure represented by Formula I(b):
4. The woven covalent organic framework of claim 1, wherein the woven framework is demetalated.
5. The woven covalent organic framework of claim 1, wherein the woven framework is metalated or re-metalated.
6. The woven covalent organic framework of claim 1, wherein the woven covalent organic framework exhibits at least an eight fold increase in elasticity when the woven covalent organic framework is de-metalated versus being metalated.
7. The woven covalent organic framework of claim 1, wherein the woven organic framework has the structure and properties of COF-505:
8. The woven covalent organic framework of claim 1, wherein the points of registry comprise tetrahedrally coordinated metal ions.
9. The woven covalent organic framework of claim 8, wherein the woven covalent organic framework has a topology selected from pnf, qtz, and sod.
10. The woven covalent organic framework of claim 8, wherein the woven covalent organic framework is de-metalated.
11. The woven covalent organic framework of claim 1, wherein the points of registry comprise octahedrally coordinated metal ions.
12. The woven covalent organic framework of claim 11, wherein the woven covalent organic framework has a topology selected from kgm and pcu.
13. The woven covalent organic framework of claim 11, wherein the woven covalent organic framework is de-metalated.
14. A resilient material comprising a woven covalent organic framework of claim 1.
15. The resilient material of claim 14, wherein the resilient material is used in shape-memory material development or biomedical applications.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a U.S. National Stage Application filed under 35 U.S.C. § 371 and claims priority from International Application No. PCT/US2016/063774, filed Nov. 25, 2016, which application claims priority under 35 U.S.C. § 119 from Provisional Application Ser. No. 62/260,458, filed Nov. 27, 2015, the disclosures of which are incorporated herein by reference.

STATEMENT REGARDING FEDERAL SPONSORED RESEARCH

This invention was supported by the U.S. Government under Grant No. DE-SC0001015 awarded by the U.S. Department of Energy and Grant No. HDTRA1-12-1-0053 awarded by the U.S. Department of Defense. The U.S. Government has certain rights in the invention.

PCT Information

Filing Document	Filing Date	Country	Kind
PCT/US2016/063774	11/25/2016	WO	00

Publishing Document	Publishing Date	Country	Kind
WO2017/091814	6/1/2017	WO	A

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	20180319821 A1	Nov 2018	US

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	Number	Date	Country
	62260458	Nov 2015	US

Covalent organic frameworks with a woven structure

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