COORDINATION POLYMERS OF COINAGE METALS SYNTHESIS AND USES THEREOF

Abstract

The embodiments described herein pertains to a new design method to produce copper, silver or gold based metal functional coordination polymers with excellent potential towards optoelectronic devices, gas storage and separation, optical sensors, and other applications.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention generally relates to coordination polymers.

2. Description of the Relevant Art

A coordination polymer is an inorganic or organometallic polymer structure containing metal cation centers linked by organic ligands. Coordination polymers are useful in a number of different applications. Some of the applications the coordination polymers are being investigated for include: optoelectronic devices (e.g., solar photovoltaic cells), molecular storage and separation applications, luminescence, electrical conductivity, magnetism, and in sensor devices.

Each application that uses a coordination polymer has its own unique requirements for the function of the coordination polymer. Ideally, the coordination polymer can be tailored to the specific use. It is therefore desirable to be able to easily create coordination polymers having different physical and chemical properties.

SUMMARY OF THE INVENTION

The embodiments described herein pertain to a new design method to produce transition and lanthanide based metal functional coordination polymers with excellent potential towards optoelectronic devices, gas storage and separation, optical sensors, and other applications. Specifically, the novel coordination compounds include transition metal and lanthanide metal coordination polymers that include at least one transition/lanthanide metal atom and at least one neutral bridging electron-donor organic ligand and/or a negatively-charged counterion. Preferably, the metal is selected from the group consisting of copper, silver and gold. The coordination polymer may, in some embodiments include an anionic ligand and/or an anionic counterion.

Specific examples of coordination polymers include coordination polymer having the structures (I)-(IV) as described herein.

The coordination polymers described herein may be used as: (1) an active component in an organic optoelectronic device; (2) a passive component in an organic optoelectronic device; (3) an active component in a metal-organic optoelectronic device; (4) a passive component in a metal-organic optoelectronic device; (5) an active component in a hybrid organic/inorganic optoelectronic device; (6) a passive component in a hybrid organic/inorganic optoelectronic device; (7) a solid-state battery material; (8) a capacitor material; (9) an optical sensor; (10) a porous solid for gas storage; (11) a porous solid for gas separation; (12) a porous solid for hazard removal; (13) a heterogeneous catalyst; and (14) a homogeneous catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of the present invention will become apparent to those skilled in the art with the benefit of the following detailed description of embodiments and upon reference to the accompanying drawings in which:

FIG. 1 depicts the solid-state absorption spectrum for poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—;

FIG. 2 depicts the solution absorption spectra for different concentrations of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— in dichloromethane;

FIG. 3 depicts the solid-state absorption spectra for the prototypical materials of polymer (P3HT) and small molecule (CuPC) OPVs overlaid with the AM0 solar spectrum;

FIG. 4 depicts the solid state absorption spectrum of poly-[Cu(PAP)₄][BF₄⁻]—;

FIG. 5 depicts absorption spectra for different concentrations of poly-[Cu(PAP)₄][BF₄⁻]— in acetonitrile;

FIG. 6 depicts the photoluminescence (PL) and PL excitation (PLE) spectra of the poly —[Cu(1,2-bis(4-pyridyl)ethane)₄][BF₄⁻]— at 298 K (RT) and 77 K;

FIG. 7 depicts the solid state absorption spectrum of poly-[Cu(1,2-bis(4-pyridyl)ethane)₄][BF₄⁻]—;

FIG. 8 depicts a TGA profile for poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—;

FIG. 9 depicts photographs of (a) a large single crystal, and (b) a thin film, of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—;

FIG. 10A depicts the structure of the repeat units in the crystal structure of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—;

FIG. 10B depicts three views of the ladder structure of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— without the free, uncoordinated, PAP ligand molecules;

FIG. 11 depicts two views of the ladder structure of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— with the free, uncoordinated, PAP ligand molecules occupying lattice sites between adjacent ladders;

FIG. 12 depicts an X-ray structure of the repeat units in the crystal structure of poly-[Cu(PAP)₄][BF₄⁻]—;

FIG. 13 depicts an X-ray structure of the repeat units in the crystal structure of poly-[Cu(4,4′-bipyridine)₄][BF₄⁻]—;

FIG. 14 depicts an X-ray structure of the metal-organic framework poly-(Pyz₂{[3,5-(CF₃)₂Pz]Cu}₂—i.e., MOF-TW1 showing: (FIG. 14A) Molecular, packing structures, and pore cross section of {Cu₂[3,5-(CF₃)₂Pz]}₂(Pyz)₂.toluene}_∞=MOF-TW1.toluene. (FIG. 14B) Pore representation of solvent-accessible regions (yellow spheres in evacuated/left and toluene-occupied/right crystals) of MOF-TW1.

FIG. 15A depicts molecular electrostatic potential (MEP) for molecular structure units in poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—;

FIG. 15B depicts selected frontier molecular orbital contours for molecular structure units in poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—;

FIG. 16 depicts an illustration of the red-shift in UV/Vis absorption bands as the structural components in poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— become more conjugated;

FIG. 17A depicts photographs of colored solids and chemical structures of each ionic functional coordination polymer with X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂ ligand=from left to right=bpa, 4,4′-bipyridine, 1,4-pyrazine, PAP, and bpe, respectively;

FIG. 17B depicts two representative crystal structures for the ionic functional coordination polymers with X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂=PAP (left) and 4,4′-bipyridine (right) with tunable pore size indicated by the guest-accessible pore volume and void % of unit cell for each; and

FIG. 17C depicts DFT simulations of the molecular electrostatic potential (MEP) on crystal structure moieties of the ionic functional coordination polymer with X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂=PAP vs. its free organic ligand.

While the invention may be susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. The drawings may not be to scale. It should be understood, however, that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but to the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention as defined by the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

It is to be understood the present invention is not limited to particular devices or methods, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include singular and plural referents unless the content clearly dictates otherwise. Furthermore, the word “may” is used throughout this application in a permissive sense (i.e., having the potential to, being able to), not in a mandatory sense (i.e., must). The term “include,” and derivations thereof, mean “including, but not limited to.” The term “coupled” means directly or indirectly connected.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

The term “alkyl” as used herein generally refers to a chemical substituent containing the monovalent group C_nH_2n, where n is an integer greater than zero. In some embodiments n is 1 to 12. The term “alkyl” includes a branched or unbranched monovalent hydrocarbon radical. Examples of alkyl radicals include, but are not limited to: methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl. When the alkyl group has from 1-6 carbon atoms, it is referred to as a “lower alkyl.” Suitable lower alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, 2-propenyl (or allyl), n-butyl, t-butyl, and i-butyl (or 2-methylpropyl).

The term “halogen” is used herein to refer to fluorine, bromine, chlorine and iodine atoms.

The term “aryl” is used to refer to an aromatic substituent which may be a single ring or multiple rings which are fused together, linked covalently, or linked to a common group such as an ethylene moiety. Aromatic ring(s) include but are not limited to phenyl, naphthyl, biphenyl, diphenylmethyl, and 2,2-diphenyl-1-ethyl. The aryl group may also be substituted with substituents including, but not limited to, alkyl groups, halogen atoms, nitro groups, carboxyl groups, alkoxy, and phenoxy to give a “substituted aryl group.” Substituents may be attached at any position on the aryl radical which would otherwise be occupied by a hydrogen atom.

The term “heterocycle” as used herein generally refers to a closed-ring structure, in which one or more of the atoms in the ring is an element other than carbon. Heterocycle may include aromatic compounds or non-aromatic compounds. Heterocycles may include rings such as thiophene, pyridine, isoxazole, phthalimide, pyrazole, indole, furan, or benzo-fused analogs of these rings. Examples of heterocycles include tetrahydrofuran, morpholine, piperidine, pyrrolidine, and others. In some embodiments, “heterocycle” is intended to mean a stable 5- to 7-membered monocyclic or bicyclic or 7- to 10-membered bicyclic heterocyclic ring which is either saturated or unsaturated, and which consists of carbon atoms and from 1 to 4 heteroatoms (e.g., N, O, and S) and wherein the nitrogen and sulfur heteroatoms may optionally be oxidized, and the nitrogen may optionally be quaternized, and including any bicyclic group in which any of the above-defined heterocyclic rings is fused to a benzene ring. In some embodiments, heterocycles may include cyclic rings including boron atoms. The heterocyclic ring may be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure. The heterocyclic rings described herein may be substituted on carbon or on a nitrogen atom if the resulting compound is stable. Also included are fused ring and spiro compounds containing, for example, the above heterocycles. The term “heteroaryl” has an equivalent meaning as heterocycle, and these terms are used interchangeably.

In one embodiment, a coordination polymer includes at least one transition metal atom or lanthanide metal atom and at least one neutral bridging electron-donor organic ligand and/or a negatively-charged counterion. In some embodiments, the coordination polymer comprises an anionic ligand. In some embodiments, the coordination polymer comprises an anionic counterion.

In one embodiment, the coordination polymer is a polymer having repeat units of the structure (I):

-{M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁}{M₂(X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂)n₂}-   (I)

• • where:
  • M₁ and M₂ are each, independently, a transition metal or a lanthanide metal;
  • X₁, X₂, Y₁, and Y₂ are each, independently N, O, P, or S;
  • each {circumflex over ( )}{circumflex over ( )}{circumflex over ( )} represents, independently, an alkyl or aryl hydrocarbon group linking the respective groups X₁/Y₁ and X₂/Y₂ together; and
  • n₁+n₂=the coordination number of M₁+the coordination number of M₂.In a preferred embodiment, M₁ and M₂ are selected from the group consisting of copper, silver and gold.In one embodiment, the coordination polymer is a polymer having repeat units of the structure (II):

-{[M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁M₂(X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂)n₂][Z₁]n₃[Z₂]n₄}-   (II)

• • where:
  • M₁ and M₂ are each, independently, a transition metal or a lanthanide metal;
  • X₁, X₂, Y₁, and Y₂ are each, independently N, O, P, or S;
  • each {circumflex over ( )}{circumflex over ( )}{circumflex over ( )} represents, independently, an alkyl or aryl hydrocarbon group linking the respective groups X₁/Y₁ and X₂/Y₂ together; and
  • n₁+n₂=the coordination number of M₁+the coordination number of M₂;
  • n₃+n₄=the oxidation state of the M₁+the oxidation state of M₂.In a preferred embodiment, M₁ and M₂ are selected from the group consisting of copper, silver and gold.In one embodiment, the coordination polymer is a polymer having repeat units of the structure (III):

-{M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁}-   (III)

• • where:
  • M₁ is a transition metal or a lanthanide metal;
  • X₁ and Y₁ are each, independently N, O, P, or S;
  • each {circumflex over ( )}{circumflex over ( )}{circumflex over ( )} represents, independently, an alkyl or aryl hydrocarbon group linking X₁ and Y₁ together; and
  • n₁ is the coordination number of M₁.In a preferred embodiment, M₁ is selected from the group consisting of copper, silver and gold.In one embodiment, the coordination polymer is a polymer having repeat units of the structure (IV):

-{[M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁][Z₁]n₃}-   (IV)

• • where:
  • M₁ and M₂ are each, independently, a transition metal or a lanthanide metal;
  • X₁ and Y₁ are each, independently N, O, P, or S;
  • each {circumflex over ( )}{circumflex over ( )}{circumflex over ( )} represents, independently, an alkyl or aryl hydrocarbon group linking the respective groups X₁ and Y₁ together; and
  • n₁ is the coordination number of M₁.
  • n₃ is the oxidation state of the M₁.In a preferred embodiment, M₁ and M₂ are selected from the group consisting of copper, silver and gold.

Transition metals (M₁ and M₂) include metals in groups 3 through 12 of the periodic table. Specific transition metals that are useful for the formation of coordination polymers include, but are not limited to: copper, silver, gold, zinc, zirconium, manganese, nickel, palladium, and platinum. Specific oxidation states of these metals are particularly useful and include, but are not limited to: Cu(I), Cu(II), Ag(I), Au(I), Au(III), Zn(II), Zr(IV), Mn(II), Ni(0), Ni(II), Pd(0), Pd(II), Pt(0), Pt(II)

In specific embodiments, M₁ and/or M₂ of the coordination polymer of any of structures (I), (II), (III), and (IV) is Cu(I).

Lanthanide metals (M₁ and M₂) include the fifteen metallic chemical elements with atomic numbers 57 through 71. Specific lanthanide metals that are useful for the formation of coordination polymers include, but are not limited to gadolinium, europium, and terbium. Specific oxidation states of these metals are particularly useful and include, but are not limited to: Gd(III), Eu(III), and Tb(III).

In specific embodiments, the compounds (X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁) and/or (X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂) of the coordination polymer of any of structures (I), (II), (III), and (IV) is a heterocycle compound having at least two heteroatoms. Examples of heterocyclic compounds having at least two heteroatoms include, but are not limited to: 1H-indazole, 1,5,2-dithiazine, 1,2,5-thiadiazole, furazan, oxazole, phenanthroline, phenarsazine, phenazine, phenothiazine, phenoxathine, phenoxazine, phthalazine, pteridine, purine, pyrazine, pyrazole (or its deprotonated pyrazolate ligand), pyridazine, bispyridine, pyrimidine, quinazoline, quinoxaline, tetrazole, thianthrene, thiazole, triazine. The heterocycle compound may be substituted or unsubstituted. In a specific embodiment, the compounds (X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁) and/or (X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂) of the coordination polymer of any of structures (I), (II), (III), and (IV) is pyrazolate, a substituted pyrazolate, pyrazine, a substituted pyrazine, bispyridine, or a substituted bispyradine.

In a specific embodiment, the compound (X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁) and/or (X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂) is a pyrazolate having the structure (V):

where each of R³, R⁴, and R⁵ is independently alkyl, halogenated alkyl, phenyl, or aryl; where the dashed lines () represent a bond to either M₁ or M₂.

Exemplary heterocyclic compounds that may be used as compound (X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁) and/or (X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂) of the coordination polymer of any of structures (I), (II), (III), and (IV) include, but are not limited to, 3,5-bis(trifluoromethyl)pyrazolate (3,5-(CF₃)₂Pz), 4,4′-azopyridine (PAP), 4,4′-bipyridine, 1,2-bis(4-pyridyl)ethane, 1,4-pyrazine, or 1,2-bis(4-pyridyl)ethylene.

In some embodiments, the compounds (X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁) and/or (X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂) of the coordination polymer of any of structures (I), (II), (III), and (IV) is a neutral bridging ligand. Exemplary neutral bridging ligands include, but are not limited to: an alkyl diamine, an alkylene diamine, a polyalkylene polyamine, and a polyimine.

In some embodiment, the coordination polymer includes an anionic counterion. Exemplary anionic counterions include, but are not limited to, anionic halogen, anionic substituted boron, and anionic substituted phosphorous.

A specific exemplary coordination polymer is the polymer:

poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)

which corresponds to the coordination polymer of structure (I) where: M₁ is Cu(I); M₂ is Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁ is 4,4′-azopyridine (PAP); X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂ is 3,5-bis(trifluoromethyl)pyrazolate (3,5-(CF₃)₂Pz), n₁ is 3; and n₂ is 1.A specific exemplary coordination polymer is the polymer:

poly-([Cu(PAP)₄][BF₄⁻])

which corresponds to the coordination polymer of structure (IV) where: M₁ is Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁ is 4,4′-azopyridine (PAP); Z₁ is BF₄; n₁ is 4; and n₃ is 1.

A specific exemplary coordination polymer is the polymer:

poly-([Cu(4,4′-bipyridine)₄][BF₄⁻])

which corresponds to the coordination polymer of structure (IV) where: M₁ is Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁ is 4,4′-bipyridine; Z₁ is BF₄; n₁ is 4; and n₃ is 1.A specific exemplary coordination polymer is the polymer:

poly-([Cu(1,2-bis(4-pyridyl)ethane)₄][BF₄⁻])

which corresponds to the coordination polymer of structure (IV) where: M₁ is Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁ is 1,2-bis(4-pyridyl)ethane; Z₁ is BF₄; n₁ is 4; and n₃ is 1.A specific exemplary coordination polymer is the polymer:

poly-([Cu(1,4-pyrazine)₄][BF₄⁻])

which corresponds to the coordination polymer of structure (IV) where: M₁ is Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁ is 1,4-pyrazine; Z₁ is BF₄; n₁ is 4; and n₃ is 1.A specific exemplary coordination polymer is the polymer:

poly-([Cu(1,2-bis(4-pyridyl)ethylene)₄][BF₄⁻])

which corresponds to the coordination polymer of structure (IV) where: M₁ is Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁ is 1,4-pyrazine; Z₁ is BF₄; n₁ is 4; and n₃ is 1.

A method general method of preparing a coordination polymer includes: mixing a transition metal compound a negatively charged counterion precursor to form am intermediate product; and mixing the intermediate product with at least one neutral bridging electron-donor organic ligand to form the coordination polymer. Suitable solvents can be used during the mixing steps. Typically organic solvents are used, including, but not limited to benzene, acetonitrile, or combinations of these solvents, depending on the solubility of the reagents.

Typically, the coordination polymer will precipitate out of the mixture as it forms. The precipitated coordination polymer is collected and dried (e.g., under vacuum).

The coordination polymers described herein may be used in a variety of applications. For example, the coordination polymers described herein may be used in an optoelectronic device. For example, the coordination polymers may be used as: an active component in an organic optoelectronic device; a passive component in an organic optoelectronic device; an active component in a metal-organic optoelectronic device; a passive component in a metal-organic optoelectronic device; an active component in a hybrid organic/inorganic optoelectronic device; or a passive component in a hybrid organic/inorganic optoelectronic device, and an organic photovoltaic cell.

The coordination polymers described herein may also be used in applications such as: solid-state batteries; capacitors; optical sensors, gas storage devices, gas separation devices, hazardous material removal devices. The coordination polymers may also be used as a heterogeneous catalyst or a homogenous catalyst.

Specific exemplary devices that the coordination polymers described herein may be used include, but are not limited to: organic photovoltaic (OPV) solar cell devices; light-emitting diodes (LEDs); room-temperature conductors/semiconductors/photoconductors; non-flammable solid-state batteries; supercapacitors; transistors; diodes; RFID tags; low-x dielectrics; single molecule magnets; MRI contrast reagent; adsorbents for fuel cells and other physisorption or chemisorption application; and sensors for various air or water pollutants.

EXAMPLES

The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.

A. Synthesis

Scheme 1 shows the synthetic route for poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂). Scheme 2 shows the general preparation strategy of (a) neutral -M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁{M₂(X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂)n₂}-, and (b) ionic -{[M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁{M₂(X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂)n₂][Z₁]n₃[Z₂]n₄}- functional coordination polymers with multiple compositional and structural variations

All manipulations were carried out under an atmosphere of purified nitrogen using standard Schlenk techniques. Dried and purified, ACS reagent grade benzene was used as a solvent to carry out the synthesis. ¹H-NMR spectra were recorded at 25° C. on a Varian 400 spectrometer; the proton chemical shifts were reported in ppm versus dichloromethane. IR spectra were recorded at 25° C. on a Shimadzu FTIR spectrometer. TGA spectra were recorded at 25° C. on a TA Q50 TGA analyzer. UV/vis/NIR and diffuse reflectance spectra were recorded on a Perkin-Elmer Lambda 900 electronic absorption spectrophotometer.

Example 1

Synthesis of Poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— Neutral Coordination Polymer

For the compound shown in Scheme 1, Cu₂O (0.19 g, 1.43 mmol) and [3,5-(CF₃)₂Pz]H (0.50 g, 2.45 mmol) were mixed in 20 mL of benzene to synthesize {[3,5-(CF₃)₂Pz]Cu}₃ based on a literature procedure (Dias, H. V. R., Polach, S. A., Wang, Z. J. Fluor. Chem. 2000, 103, 163, which is incorporated herein by reference). The mixture was filtered and the filtrate was collected. {[3,5-(CF₃)₂Pz]Cu}₃ (0.1 g, 1 mmol) and 4,4′-azopyridine (PAP) (0.071 g, 3 mmol) were mixed in benzene (10 mL). A black product started to form instantly. The product was collected using vacuum filtration and further dried under vacuum for 2 hours. The black product obtained (melting point=165° C.) has no luminescence. The product was very soluble in acetone, acetonitrile, tetrahydrofuran (THF) and dichloromethane (DCM). The crystals were grown in acetonitrile using slow evaporation for 2 days under nitrogen atmosphere at 25° C. to obtain X-ray quality crystals. ¹H-NMR (reference to DCM) δ/ppm: 7.1 correspond to Pz (C—H), 7.4, 7.8 and 8.8 correspond to PAP (C—H). IR: aromatic C—H stretch: 3133.38 cm⁻¹, aliphatic C—H stretch: 3023.29 cm⁻¹, C═N stretch: 2292.52 cm⁻¹, N=N stretch: 2119.19 cm⁻¹, aromatic C=C bend: 1592.19 cm⁻¹, aromatic C—C stretch: 1561.74 cm⁻¹.

Example 2

Synthesis of Poly-[Cu(PAP)₄][BF₄⁻]— ionic coordination polymer

This embodiment corresponds to the Scheme 2(b) variable of an ionic functional coordination polymer:

-{[M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁][Z₁]n₃}-

Where: M₁=Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=PAP; Z₁=BF₄⁻; n₁=4, and n₃=1.

For this compound, [Cu(CH₃CN)₄][BF₄⁻] (0.1 g, 1 mmol) was prepared based on a literature procedure (Kubas, G. J. Inorg. Synth. 1979, 19, 90, which is incorporated herein by reference) and 4,4′-azopyridine (PAP) (0.234 g, 4 mmol) were mixed in acetonitrile (10 mL). A black product started to form in 2 hours. The product was collected using vacuum filtration and further dried under vacuum for 2 hours. The black product obtained (melting point=380-385° C.) has no luminescence. The product was soluble in acetonitrile. The crystals were grown in acetonitrile using slow evaporation for 2 days under nitrogen atmosphere at 25° C. to obtain X-ray quality crystals. ¹HNMR (reference to acetonitrile) 6/ppm: 7.7, 7.8 and 8.8 correspond to PAP (C—H). IR: aromatic C—H stretch: 3098.24 cm⁻¹, aliphatic C—H stretch: 3060.77 cm⁻¹, C═N stretch: 322.97 cm⁻¹, N═N stretch: 2105.14 cm⁻¹, aromatic C═C bend: 1590.19 cm⁻¹, aromatic C—C stretch: 1557.06 cm⁻¹.

Example 3

Synthesis of Poly-[Cu(4,4′-bipyridine)₄][BF₄⁻]— Ionic Coordination Polymer

This embodiment corresponds to the Scheme 2(b) variable of an ionic functional coordination polymer:

-{[M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁][Z₁]n₃}-

Where: M₁=Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=4,4′-bipyridine; Z₁═BF₄⁻; n₁=4, and n₃=1.

For this compound, [Cu(CH₃CN)₄][BF₄⁻] (0.1 g, 1 mmol) was prepared based on a literature procedure (Kubas, G. J. Inorg. Synth. 1979, 19, 90, which is incorporated herein by reference) and (4,4′-bipyridine) (0.198 g, 4 mmol) were mixed in acetonitrile (10 mL). An orange product started to form in 2 hours. The product was collected using vacuum filtration and further dried under vacuum for 2 hours. The orange product obtained (melting point=360-365 δC(dec)) has no luminescence. The product was soluble in acetonitrile. The crystals were grown in acetonitrile using slow evaporation for 2 days under nitrogen atmosphere at 25° C. to obtain X-ray quality crystals. ¹H-NMR (reference to acetonitrile) δ/ppm: 7.7 and 8.6 correspond to bpy (C—H). IR: aromatic C—H stretch: 3040.02 cm⁻¹, aliphatic C—H stretch: 3029.40 cm⁻¹, C═N stretch: 2250.81 cm⁻¹, aromatic C═C bend: 1604.33 cm⁻¹, aromatic C—C stretch: 1554.72 cm⁻¹.

Example 4

Synthesis of Poly-[Cu(1,2-bis(4-pyridyl)ethane)₄][BF₄⁻]— Ionic Coordination Polymer

This embodiment corresponds to the Scheme 2(b) variable of an ionic functional coordination polymer:

-{[M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁][Z₁]n₃}-

Where: M₁=Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=1,2-bis(4-pyridyl)ethane; Z₁═BF₄⁻; n₁=4, and n₃=1.

For this compound, [Cu(CH₃CN)₄][BF₄⁻] (0.1 g, 1 mmol) was prepared based on a literature procedure (Kubas, G. J. Inorg. Synth. 1979, 19, 90, which is incorporated herein by reference) and 1,2-Bis(4-pyridyl)ethane (0.234 g, 4 mmol) were mixed in acetonitrile (10 mL). A white-yellowish product started to form in 2 hours. The product was collected using vacuum filtration and further dried under vacuum for 2 hours. The white-yellowish product obtained (melting point=260 6C (dec)) has yellow luminescence. The product was soluble in acetonitrile. Several attempts of crystallization were unsuccessful in producing suitable crystals because of its high sensitivity to air. ¹H-NMR (reference to acetonitrile) δ/ppm: 2.9, 7.3 and 8.5 correspond to bpa (C—H). IR: aromatic C—H stretch: 3042.03 cm⁻¹, aliphatic C—H stretch: 2931.95 cm¹, C═N stretch: 2252.70 cm⁻¹, aromatic C═C bend: 1596.88 cm⁻¹, aromatic C—C stretch: 1554.72 cm⁻¹.

Example 5

Synthesis of Poly-(Pyz_n1{[3,5-(CF₃)₂Pz]Cu}n₂)—Neutral Coordination Polymers and Metal-Organic Frameworks

These embodiments correspond to the three Scheme 3 variables of neutral functional coordination polymers of copper(I):

Synthesis of 1. Both solventless and solvent-mediated transformations attained this product. One solventless route entailed 1:3 molar ratio of [3,5-(CF₃)₂Pz]Cu₃ (0.1 g) and pyrazine (0.034 g) being mixed in a closed vial where they were left to react. Due to the fact that pyrazine sublimes as well at room temperature and ambient pressure, it reacts in the gas phase via the vapor of its solid with the less volatile {[3,5-(CF₃)₂Pz]Cu}₃ cyclotrimer solid, resulting in a color change of the white copper timer immediately to yellow, orange, and ultimately maroon—gradually as time goes by. The reaction starts occurring in a minute time scale and takes approximately 20 min to completion. The solventless route can be further accelerated by mechanical grinding of the same stoichiometric amounts, whereby the reaction starts occurring instantly and is completed within a minute time scale. The maroon product obtained was very soluble in acetone and acetonitrile, among other common organic solvents. Finally, the solvent-mediated route involved the reaction of a 1:3 molar ratio of {[3,5-(CF₃)₂Pz]Cu}₃ (0.097 g) and pyrazine (0.0336 g) in 10 mL of benzene. The solution color changed immediately to orange. The resulting product was obtained by removing the solvent under reduced pressure and further dried by vacuuming for extra 2 hrs. X-ray quality crystals were obtained from hot benzene/dichloromethane. M.p. 180° C. ¹H-NMR using as reference acetonitrile d₃δ resulted in the following resonances: 6.98 ppm (Pz^F, C—H), 8.70 ppm (Pyz, C—H). IR: 2134.15 cm⁻¹ (C═N stretch), 1940.45 cm⁻¹ (aromatic C═C bend), 1509.64 cm⁻¹ (aromatic C—C stretch), 3094.25 cm⁻¹ (aromatic C—H stretch). Anal. Calcd. for C₄₂ H₁₈ Cu₆ F₃₆N₁₈: C, 27.42; H, 0.99; N, 13.70%. Found C, 27.07; H, 0.81; N, 13.35% (without dichloromethane).

Synthesis of 2. The reaction entailed a 1:1:3 molar ratio of {[3,5-(CF₃)₂Pz]Cu}₃ (0.097 g), {[3,5-(CF₃)₂Pz]Ag}₃ (0.1 g), and pyrazine (0.0336 g), all mixed in 10 mL of benzene. The color of solution changed immediately to light orange. The reaction was stirred for 6 hours. The resulting product was obtained by removing solvent using vacuum and further dried by vacuuming for extra 2 hours. The product was soluble in most of organic solvents, including benzene and acetonitrile. X-ray quality crystals were obtained from hot toluene. M.p. 160° C. ¹H-NMR using as reference acetonitrile d₃δ resulted in the following resonances: 7.40 ppm (Pz^F C—H), 8.70 ppm (Pyz, C—H). IR: 2964.25 cm⁻¹ (aromatic C—H stretch), 2049.15 cm⁻¹ (C═N stretch), 1695.45 cm⁻¹ (aromatic C═C bend), 1519.64 cm⁻¹(aromatic C—C stretch). Anal. Calcd. for C₁₈ H₁₀ Cu₂ F₁₂ N₈: C, 31.18; H, 1.45; N, 16.16%. Found: C, 30.66; H, 1.37; N, 15.65%. (without toluene).

Synthesis of 3. A 1:1 molar ratio reaction was carried out whereby {[3,5-(CF₃)₂Pz]Cu}₃ (0.1 g) and {Ag₆[3,5-(CF₃)₂Pz]₆(Pyz)₂(benzene)₂} (0.27 g—synthesized following the same procedure below for complex 4) were mixed in 10 mL of benzene. A light yellow color started to form immediately. The reaction was stirred for 2 hours. The resulting product was obtained by removing solvent using vacuum for 2 hours. The light yellow solid product obtained has no luminescence. The product was very soluble in organic solvents, such as benzene, acetone and acetonitrile. X-ray quality crystals were obtained from hot benzene. M.p. 155° C. ¹H-NMR using as reference acetonitrile d₃δ resulted in the following resonances: 7.00 ppm (Pz^F, C—H), 8.56 ppm (Pyz, C—H), IR: 2964.25 cm⁻¹(aromatic C—H stretch), 2049.15 cm⁻¹ (C═N stretch), 1785.45 cm⁻¹ (aromatic C═C bend), 1619.64 cm⁻¹ (aromatic C—C stretch). Anal. Calcd. for C₂₄ H₁₂ Cu₃ F₁₈ N₉: C, 30.06; H, 1.26; N, 13.14%. Found: C, 30.18; H, 1.34; N, 13.98% (without benzene).

Example 6

Synthesis of Poly-([(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)]_n1{[3,5-(CF₃)₂Pz]Ag}_n2)—Neutral Coordination Polymers and Oligomers

These embodiments correspond to the two Scheme 4 variables of neutral functional coordination oligomer 4 and coordination polymer 5 of silver(I):

Synthesis of 4. A 1:3 molar ratio reaction was carried out whereby {[3,5-(CF₃)₂Pz]Ag}₃ (0.1 g) and pyrazine (0.028 g) were mixed in dichloromethane (10 mL). The reaction was stirred for 2 hours. The resulting product was obtained by removing solvent using vacuum for 2 hours. The white product obtained has blue luminescence. The product was partially soluble in organic solvents, such as acetonitrile and acetone. X-ray quality crystals were obtained from dichloromethane by slow evaporation. M.p. 170° C. ¹H-NMR using as reference acetonitrile d₃δ resulted in the following resonances: 7.3 ppm (Pz^F, C—H), 8.70 ppm (Pyz, C—H). IR: 3160.06 cm⁻¹(aromatic C—H stretch), 2165 cm⁻¹ (C═N stretch), 2170.45 cm⁻¹ (aromatic C═C bend), 1972.38 cm⁻¹ (aromatic C—C stretch). Anal. Calcd. for C₃₈ H₁₄ Ag₆ F₃₆ N₁₆: C, 22.53; H, 0.70; N, 11.06%. Found: C, 21.66; H, 0.33; N, 10.70% (without 2 molecules of benzene).

Synthesis of 5. A 1:3 molar ratio reaction was carried out whereby {[3,5-(CF₃)₂Pz]Ag}₃ (0.1 g) and piperazine (Ppz) (0.066 g) were mixed in dichloromethane (10 mL); varying the molar ratio to 1:6 or 1:2 attained the same subsequent observations. The reaction was stirred for 2 hours. The product was collected using vacuum filtration and further dried under vacuuming for 2 hours. The white product obtained has no luminescence. The product was insoluble in most organic solvents, such as benzene and dichloromethane, but it is partially soluble in acetonitrile. Using sonication and filtration was essential to acquire the best result for recrystallization. X-ray quality crystals were obtained from acetonitrile by slow evaporation. M.p. 250° C. (dec.). ¹H-NMR using as reference acetone d₆δ resulted in the following resonances: 7.1 ppm (Pz^F, C—H), 2.85 ppm (Ppz, C—H₂), 1.90 ppm (Ppz, N—H). IR: 3276.73 cm⁻¹ (N—H stretch), 3020.98 cm⁻¹ (aromatic C—H stretch), 2847.67 cm⁻¹ (aliphatic C—H stretch), 2353.23 cm⁻¹ (C═N stretch), 1531.90 cm⁻¹ (aromatic C═C bend), 1433.83 cm⁻¹ (aromatic C—C stretch). Anal. Calcd. for C₁₄ H₁₂ Ag₂ F₁₂N₆: C, 23.75; H, 1.71; N, 11.87%. Found: C, 23.07; H, 0.89; N, 11.12%.

Example 7

Synthesis of Poly-[Cu(1,4-pyrazine)₂(acetonitrile)₂][BF₄⁻]— Ionic Coordination Polymer

This embodiment corresponds to the Scheme 2(b) variable of an ionic functional coordination polymer:

-{[M₁(X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁)n₁][Z₁]n₃}-

Where: M₁=Cu(I); X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=1,4-pyrazine; Z₁═BF₄⁻; n₁=2, and n₃=1, as shown in Scheme 5.

Synthesis of 6. A 1:2 (or 1:4) molar ratio reaction was carried out whereby [Cu(MeCN)₄]BF₄ (0.1 g) and pyrazine (Pyz) (0.05 g) were mixed in a closed vial where they were left to react. Due to the fact that pyrazine sublimes at room temperature, [Cu(MeCN)₄]BF₄ reacts with pyrazine in the gas phase resulting in a color change of the white copper precursor immediately to yellow. The product was soluble only in acetonitrile. The yellow product was crystalized using acetonitrile and slow evaporation for 2 days under inert atmosphere using purified nitrogen gas to obtain X-ray quality single crystals. M.p.>500° C. ¹H-NMR using as reference acetonitrile d₃δ resulted in the following resonances: 8.4 ppm (Pyz, C—H). IR: 2102.80 cm⁻¹ (C═N stretch), 1976.32 cm⁻¹ (aromatic C═C bend), 1592.19 cm⁻¹ (aromatic C—C stretch), 3058.43 cm⁻¹ (aromatic C—H stretch). Anal. Calcd. for C₈ H₁₀ B Cu F₄ N₄: C, 30.74; H, 3.23; N, 17.93%. Found: C, 31.04; H, 2.68; N, 17.94.

B. Spectral Properties

Here we provide a discussion of the spectral properties of three examples of preferred embodiments with an extensive discussion of how one embodiment compares favorably with the state of the art for its use in solar cell applications.

Absorption Properties of Poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— Neutral Coordination Polymer

FIG. 1 shows the solid-state absorption spectrum for one preferred embodiment, poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—, which covers the entire UV and visible spectral range as well as a broad NIR range. FIG. 2 shows the solution absorption spectra for different concentrations of the same poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— in dichloromethane. The absorption in the UV region is due to ligand π-π* transitions, which appear at low concentration at similar wavelengths to those for the free PAP ligand, whereas metal-to-ligand charge transfer (MLCT) bands appear at longer wavelengths in the visible region at high concentration. In the solid-state, both π-π* and MLCT bands appear and the absorption range is extended to longer wavelengths in the visible and near-IR regions. Dissolving the solid re-generates the yellow or orange solution colors and, likewise, evaporating the solvent from solutions re-generates the black-colored solid. These properties suggest that the solid form offers a platform for extended 1D or 2D conjugation of unsaturated organic and metal units, where these chromophores are in electronic communication with one another, whereas in solution the extent of the conjugation occurs over only a few molecules in smaller cluster/oligomer aggregates (as opposed to infinite chains or sheets in the solid state).

By looking at the diffuse reflectance spectra in FIG. 1, the poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— is be able to absorb the radiation in the entire solar spectral region from 200 to 1200 nm. The absorption properties of the solid product are close to the solar cells of nanostructure properties which have attracted much attention due to the high ability of absorbing 94% of the visible light (400-800 nm wavelength range) in the so-called “nanodome solar cells” made from a thick (280 nm) nano-patterned layer of hydrogenated amorphous silicon (a-Si:H) vs 65% for typical a-Si—H solar cells based on flat thin films. The poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—, in comparison, exhibits near-100% overlap with not only the visible light but also the UV portion of sunlight within 200-400 nm as well as significant overlap with the near-infrared (NIR) solar radiation within 800-1200 nm that a-Si:H or even crystalline silicon solar cells do not perform nearly as well in terms of NIR absorption. This behavior believed to be due to the optical bandgap being ˜1200 nm for poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— vs ˜900 nm for Si. The spectral properties of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— are also superior to those of more conventional organic solar cell materials, such as poly(3-hexyl)thiophene (P₃HT) and metal phthalocyanines (e.g., copper(II) phthalocyanine; i.e., CuPc), the prototypical light-absorbing materials used in polymer and small-molecule OPVs, respectively. FIG. 3 shows the solid-state absorption spectra of these conventional materials overlaid with the AM0 solar light. Inspection of this figure immediately points out the major problem with P3HT and phthalocyanine solar cells: the poor overlap of their absorption with significant portions of the ultraviolet/visible/near-infrared (UV/Vis/NIR) regions of the solar radiation makes it clear why their peak device efficiencies continue to dwell around ˜5-9% or lower. These values are well-below those achieved for other types of solar cells including:

(a) Hybrid organic-inorganic solar cells: In particular, dye-sensitized solar cells (DSSCs), typically based on colloidal wide-bandgap semiconductors such as TiO₂ or SnO₂ tethered with Ru(II) and Pt(II) polypyridyl complexes as photosensitizers, have attained 11-12% records; replacing those expensive metal centers with the metal center of choice in this invention—i.e., Cu(I)—resulted in a drastic efficiency decrease due to a rather poor overlap of their absorption spectra with the solar spectrum vs the overlap for the analogous Ru(II) or Pt(II) sensitizers or the poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— (FIG. 1).

(b) Inorganic solar cells: Record efficiencies of ˜30% have been attained for crystalline and ˜12-13% for amorphous silicon solar cells, ˜40% for multi-junction germanium solar cells, ˜28% for III-V semiconductor solar cells (e.g., InAs and GaAs cells), ˜17.3% for other binary inorganic semiconductor solar cells besides those of III-V—such as those based on cadmium telluride (CdTe), and ˜19.6% for ternary (as opposed to binary) inorganic semiconductor solar cells—such as those based on cadmium indium selenide (CIS), and ˜22.1% for the perovskite solar cells—which are most commonly based on lead (Pb) salts.

Absorption Properties of Poly-[Cu(PAP)₄][BF₄⁻]— Ionic Coordination Polymer

FIG. 4 depicts the solid state absorption spectrum of poly-[Cu(PAP)₄][BF₄⁻]—. FIG. 5 depicts absorption spectra for different concentrations of poly-[Cu(PAP)₄][BF₄⁻]— in acetonitrile.

Absorption Properties of Poly-[Cu(1,2-bis(4-pyridyl)ethane)₄][BF₄⁻]— Ionic Coordination Polymer

FIG. 6 depicts the photoluminescence (PL) and PL excitation (PLE) spectra of the poly —[Cu(1,2-bis(4-pyridyl)ethane)₄][BF₄⁻]— at 298 K (RT) and 77 K. FIG. 7 depicts solid state absorption spectrum of the poly-[Cu(1,2-bis(4-pyridyl)ethane)₄][BF₄].

C. Material Properties

FIG. 8 shows the thermogravimetric analysis (TGA) profile for poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— to illustrate the thermal stability of the material. FIG. 9 shows two solid-state forms of the material (poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—) that are conducive for device use, a large single crystal plate (akin to those used for Si chips in the microelectronics industry) and a thin film form (akin to those used in nanoscale organic electronic devices, such as OLEDs and OPVs). The large single crystal form can be used either as is, akin to single-crystal based organic electronic devices, or by slicing it into wafers akin to those used for Si chips in the microelectronics industry.

Preliminary solar cell device testing results on poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— have shown that only the neat solid form produces a photocurrent, whereas doped solid forms do not (besides that of the host matrix). Thus, the uses of this and other embodiments in this class of coordination polymer materials in solar cell devices shall focus on neat solid forms such as neat thin films and single crystals.

D. Structural Properties

FIGS. 10-11 show multiple views of the X-ray crystal structure of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—, while Table 1 shows the unit cell data. FIG. 10A depicts the structure of the repeat units in the crystal structure of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—. FIG. 10B depicts three views of the ladder structure of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— without the free, uncoordinated, PAP ligand molecules. FIG. 11 depicts two views of the ladder structure of poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)— with the free, uncoordinated, PAP ligand molecules occupying lattice sites between adjacent ladders. These data clearly illustrate the 1D and 2D conjugation of the chromophoric components, which is responsible for the aforementioned conducting and absorption properties for their corresponding solids.

FIG. 12 depicts an X-ray structure of the repeat units in the crystal structure of poly-[Cu(PAP)₄][BF₄⁻]—.

FIG. 13 depicts an X-ray structure of the repeat units in the crystal structure of poly-[Cu(4,4′-bipyridine)₄][BF₄⁻]—.

FIG. 14 depicts an X-ray structure of the metal-organic framework poly-(Pyz₂{[3,5-(CF₃)₂Pz]Cu}₂—i.e., complex 2=MOF-TW1 in Scheme 3 showing: (a) Molecular, packing structures, and pore cross section of {Cu₂[3,5-(CF₃)₂Pz]}₂(Pyz)₂.toluene}_∞(2.toluene=MOF-TW1.toluene). (b) Pore representation of solvent-accessible regions (yellow spheres in evacuated/left and toluene-occupied/right crystals) of MOF-TW1. The pore characteristics of toluene-free cavities include the following features:

i) Total potential solvent-accessible volume is 416.4 ų, representing 27.10% of the 1535.05(13) A3 unit cell volume, as calculated by Platon.

ii) Surface area=1278 m²/g, as calculated by Materials Studio.

iii) Pore size of ˜13.9 Å×5.4 Å, as measured by Mercury, corresponding to the dimensions of the parallelogram-shaped channel cross sections (as shown in FIG. 14a, whereas the yellow spheres in FIG. 14b exhibit a diameter that corresponds to the 5.4 Å shorter distance).

TABLE 1
Crystal data and structure refinement for poly-
(PAP3{[3,5-(CF3)2Pz]Cu}2)-
Empirical formula               C35H22Cu2F12N14
Formula weight                  993.75
Temperature                     100(2) K
Wavelength                      0.71073 Å
Crystal system                  Monoclinic
Space group                     P 21/c
Unit cell dimensions            a = 17.2721(12) Å α = 90°
                                b = 16.2368(12) Å β = 105.2370(10)°
                                c = 14.1727(10) Å γ = 90°
Volume                          3834.9(5) Å3
Z                               4
Density (calculated)            1.721 Mg/m3
Absorption coefficient          1.217 mm−1
F(000)                          1984
Crystal size                    0.31 × 0.27 × 0.06 mm3
Theta range for data collection 1.75 to 27.12°
Index ranges                    −22 <= h <= 22, −20 <= k <=
                                20, −18 <= l <= 18
Reflections collected           51407
Independent reflections         8459 [R(int) = 0.0316]
Completeness to theta = 27.12°  99.7%
Absorption correction           Semi-empirical from equivalents
Max. and min. transmission      0.9350 and 0.7071
Refinement method               Full-matrix least-squares on F2
Data/restraints/parameters      8459/0/568
Goodness-of-fit on F2           1.021
Final R indices [I > 2sigma(I)] R1 = 0.0287, wR2 = 0.0749
R indices (all data)            R1 = 0.0343, wR2 = 0.0785
Largest diff. peak and hole     2.305 and −0.636 e.Å−3

R ₁ =Σ∥F _o |−|F _c ∥/|Σ|F _o |; wR ₂={Σ[w(F_o²−wF_c²)²/Σ[w(F_o²)²]}^1/2

TABLE 2
Crystal data and structure refinement for poly-[Cu(PAP)4][BF4−]-
Empirical formula               C40H32B8Cu2F16N16
Formula weight                  1254.38
Temperature                     220(2) K
Wavelength                      0.71073 Å
Crystal system                  Tetragonal
Space group                     I 4 1/a
Unit cell dimensions            a = 17.402(3) Å α = 90°
                                b = 17.402(3) Å β = 90°
                                c = 7.6865(12) Å γ = 90°
Volume                          2327.6(6) Å3
Z                               2
Density (calculated)            1.790 Mg/m3
Absorption coefficient          1.034 mm−1
F(000)                          1252
Crystal size                    0.26 × 0.25 × 0.16 mm3
Theta range for data collection 2.90 to 27.09°.
Index ranges                    −22 <= h <= 22, −22 <= k <=
                                22, −9 <= l <= 9
Reflections collected           15262
Independent reflections         1280 [R(int) = 0.0223]
Completeness to theta = 27.09°  99.8%
Absorption correction           Semi-empirical from equivalents
Max. and min. transmission      0.8521 and 0.7770
Refinement method               Full-matrix least-squares on F2
Data/restraints/parameters      1280/2/93
Goodness-of-fit on F2           1.026
Final R indices [I > 2sigma(I)] R1 = 0.0474, wR2 = 0.1327
R indices (all data)            R1 = 0.0487, wR2 = 0.1346
Largest diff. peak and hole     0.290 and −0.547 e.Å−3

TABLE 3
Crystal data and structure refinement
for poly-[Cu(4,4′-bipyradine)4][
BF4−]-
Empirical formula               C20H16BCuF4N4
Formula weight                  462.72
Temperature                     220(2) K
Wavelength                      0.71073 Å
Crystal system                  Monoclinic
Space group                     P 21/c
Unit cell dimensions            a = 7.1238(3) Å α = 90°
                                b = 16.3335(7) Å β = 100.469(2)°
                                c = 17.2929(8) Å γ = 90°
Volume                          1978.65(15) Å3
Z                               4
Density (calculated)            1.553 Mg/m3
Absorption coefficient          1.155 mm−1
F(000)                          936
Crystal size                    0.17 × 0.05 × 0.03 mm3
Theta range for data collection 1.73 to 27.10°
Index ranges                    −9 <= h <= 8, −20 <= k <=
                                20, −22 <= l <= 22
Reflections collected           30862
Independent reflections         4358 [R(int) = 0.0533]
Completeness to theta = 27.10°  99.9%
Absorption correction           Semi-empirical from equivalents
Max. and min. transmission      0.9629 and 0.8235
Refinement method               Full-matrix least-squares on F2
Data/restraints/parameters      4358/0/271
Goodness-of-fit on F2           1.027
Final R indices [I > 2sigma(I)] R1 = 0.0580, wR2 = 0.1449
R indices (all data)            R1 = 0.0803, wR2 = 0.1567
Largest diff. peak and hole     0.779 and −0.500 e.Å−3

TABLE 4
Crystallographic data for complexes 1-6 shown in Schemes 3-5.
Complex	[1]•CH2Cl2	[2]•toluene	[3]•1.5benzene	[4]•2benzene	[5]	[6]
CCDC	1821487	1821694	1821488	1821489	1821705	1821704
Crystal	Triclinic	Triclinic	Triclinic	Triclinic	Monoclinic	Orthorhombic
system
Formula	C43H20Cl2Cu6F36N18	C25H18Cu2F12N8	C30H18Cu3F18N9	C50H26Ag6F36N16	C14H12Ag2F12N6	C8H10BCuF4N4
Formula	1924.91	785.55	1037.15	2182.09	708.04	312.55
weight
Space	P1	P1	P1	P1	C2/c	Pbca
group
a, (Å)	11.023	(5)	9.8425	(5)	11.9433	(6)	10.537	(4)	15.056	(2)	10.709	(2)
b, (Å)	11.174	(5)	12.2763	(6)	13.2270	(6)	11.355	(4)	27.738	(3)	10.614	(2)
c, (Å)	14.641	(11)	13.2130	(6)	15.0253	(11)	15.527	(5)	12.0564	(14)	22.430	(4)
α, (deg)	103.763	(12)	83.306	(1)	98.870	(1)	98.364	(5)	90	90
β, (deg)	104.969	(11)	85.895	(1)	108.650	(1)	105.997	(5)	121.855	(2)	90
γ, (deg)	106.907	(8)	75.710	(1)	116.392	(1)	106.056	(5)	90	90
V, (Å3)	1568.2	(16)	1535.05	(13)	1887.8	(2)	1666.0	(9)	4276.8	(9)	2549.6	(7)
Z	1	2	2	1	8	8
T, (K)	100	(2)	200	(2)	200	(2)	200	(2)	100	(2)	220	(2)
λ, (Å)	0.71073	0.71073	0.71073	0.71073	0.71073	0.71073
ρcalcd,	2.028	1.700	1.825	2.175	2.199	1.629
(Mg/m3)
μ, (mm−1)	2.241	1.490	1.801	1.880	1.950	1.748
Crystal size,	0.20 × 0.08 ×	0.22 × 0.14 ×	0.36 × 0.23 ×	0.32 × 0.13 ×	0.21 × 0.20 ×	0.12 × 0.10 ×
(mm3)	0.08	0.03	0.11	0.12	0.07	0.09
Absorption	multi-scan	multi-scan	multi-scan	multi-scan	multi-scan	multi-scan
correction
Abs. Corr.	0.8446/0.6590	0.9637/0.7343	0.8293/0.5641	0.8045/0.5837	0.8837/0.6883	0.8530/0.8151
factor
Total	14320	15834	25717	15589	28523	25124
reflections
Independ.	6247	6782	8298	7118	4718	2747
Reflections
Data/res/	6247/0/484	6782/0/425	8298/0/541	7118/9/503	4718/0/315	2747/0/165
parameters
R1 [I >	0.0365	0.0343	0.0424	0.0649	0.0201	0.0258
2σ(I)]
wR2 [I >	0.0940	0.0873	0.1199	0.1590	0.0601	0.0757
2σ(I)]
R1 (all	0.0475	0.0494	0.0531	0.0898	0.0220	0.0353
data)
wR2 (all	0.1022	0.0950	0.1291	0.1831	0.0621	0.0820
data)
GOF on F2	1.043	1.032	1.032	1.032	1.023	1.028
Δρ(max),	1.338, −1.351	0.517, −0.489	1.005, −0.639	1.805, −1.822	1.064, −0.679	0.239, −0.389
Δρ(min)
(e/Å3)

E. Theoretical Manifestation of Optoelectronic Properties

FIGS. 15 and 16 show computational data that substantiate the optoelectronic properties upon extended conjugation in for poly-(PAP₃{[3,5-(CF₃)₂Pz]Cu}₂)—. Thus, as the structural components become more conjugated, the conductivity increases for electrons and holes—blue and red parts, respectively, in FIG. 15A—as well as excitons—FIG. 15B—while the absorption bands red-shift FIG. 16.

Members of this series of functional coordination polymers with tetrahedral building blocks corresponding to those shown in Scheme 2(a) and 2(b) above for neutral and ionic functional coordination polymers, respectively. We have synthesized a series of exemplary embodiments for the ionic functional coordination polymers of Scheme 2(b) above, whereby M1=M2=Cu(I); n1=n2=4, Z1═Z2═[BF4]⁻, n3=n4=1, and whereby X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂=the bridging diimine linkers being the “back-to-back” diimine bridging ligands shown in FIG. 15A, namely—from left to right=1,2-bis(4-pyridyl)ethane, 4,4′-bipyridine, 1,4-pyrazine, PAP, or 1,2-bis(4-pyridyl)ethylene, respectively. FIG. 17A also shows photographs of the colored solids obtained for member of this series. Remarkably, the visible colors are obtained for such solids although the absorption maximum of both the ligands and the d¹⁰ metal ion are in the UV region. The observation of visible colors in these preferred ionic functional coordination polymer embodiments, therefore, represent an inorganic structural analogy to the structure of vegetables such as carrots and tomatoes whose colors are exhibited due to oligomeric conjugation of the far-UV-absorbing ethylene moieties, shifting λ_max from 190 nm to ˜450 and 500 nm, respectively, due to the 11 and 13 conjugated double bonds in β-carotene and lycopene, respectively. This series' members, likewise, exhibit conjugation of stronger (aromatic) chromophores than ethylene in an extended infinite matter (as opposed to merely oligomeric) across the four directions of the tetrahedral arms of the Cu(I) centers. The degree of red shift into the visible region depends on the size of the chromophoric aromatic ligands that are conjugated indefinitely to one another through the d¹⁰ metal center; an extreme situation leads, most remarkable, to a black absorber in the preferred embodiment with X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂=PAP, which exhibits continuous absorption of all visible and UV wavelengths of the solar spectrum and a broad region of the near-IR portion, e.g., 900 nm. In another extreme, when the chromophoric diamine ligand has a saturated moiety separating its two pyridyl aromatic rings, which is the case in the preferred embodiment with X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂=1,2-bis(4-pyridyl)ethane, the conjugation is broken and a faint-yellow solid form for that coordination polymer, which then exhibits a different set of functional properties including bright luminescence with near-UV excitation (instead of strong visible absorptions) and reduced electronic conductivity desired for supercapacitors and battery compositions. These are examples of other functional material properties for this ionic functional coordination polymer family, which include not only being potential candidates for (a) “black absorbers” for photovoltaic or other electronic device applications in view of the properties illustrated in FIGS. 17A, and 17B selective guest adsorption due to their tunable porosity depending upon the size of the ligand—FIG. 16B—but also concomitant (c) light-emitting diode (LED) applications due to their bright luminescence, and (d) battery/supercapacitor applications in part due to the low electrical conductivity yet high ionic conductivity because the disordered BF₄⁻ ions that fill the pores of the cationic metal-organic frameworks are essentially unbound, hence they are expected to exhibit extremely high ionic mobility. Battery applications, for example, will be pursued for further modifications of such ionic functional coordination polymers whereby the BF₄⁻ counterions are exchanged with smaller F⁻ and/or ubiquitous Cl⁻ anions for potential next-generation batteries that may not be as flammable as lithium ion batteries. The MEP pictures in FIG. 17C from DFT simulations of crystal structure moieties of the ionic functional coordination polymer with X₁{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₁=X₂{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y₂=PAP vs. its free organic ligand illustrate the increased propagation of polarons upon proceeding from the uncoordinated organic ligand molecule to the extended solid-state structure—which is deduced by contrasting the more “green” or less “blue”/less positive MEP magnitude for the ligand in comparison with the situation upon increased conjugation with metal-ligand molecular units in FIG. 17C—which is promising for the highly-coveted n-type (electrontransporting) semiconducting behavior in organic electronic devices.

In this patent, certain U.S. patents, U.S. patent applications, and other materials (e.g., articles) have been incorporated by reference. The text of such U.S. patents, U.S. patent applications, and other materials is, however, only incorporated by reference to the extent that no conflict exists between such text and the other statements and drawings set forth herein. In the event of such conflict, then any such conflicting text in such incorporated by reference U.S. patents, U.S. patent applications, and other materials is specifically not incorporated by reference in this patent.

Further modifications and alternative embodiments of various aspects of the invention will be apparent to those skilled in the art in view of this description. Accordingly, this description is to be construed as illustrative only and is for the purpose of teaching those skilled in the art the general manner of carrying out the invention. It is to be understood that the forms of the invention shown and described herein are to be taken as examples of embodiments. Elements and materials may be substituted for those illustrated and described herein, parts and processes may be reversed, and certain features of the invention may be utilized independently, all as would be apparent to one skilled in the art after having the benefit of this description of the invention. Changes may be made in the elements described herein without departing from the spirit and scope of the invention as described in the following claims.

Claims

1. A coordination polymer comprising: at least one metal atom selected from the group consisting of copper, silver, and gold; andat least one neutral bridging electron-donor organic ligand and/or a negatively-charged counterion.

2. The coordination polymer of claim 1, wherein the coordination polymer comprises an anionic ligand.

3. The coordination polymer of claim 1, wherein the coordination polymer comprises an anionic counterion.

4. The coordination polymer of claim 1, wherein the coordination polymer is a polymer having repeat units of the structure (I): -{M1(X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1)n1}{M2(X2{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y2)n2}-   (I)where:M1 and M2 are each, independently, copper, silver, or gold;X1, X2, Y1, and Y2 are each, independently N, O, P, or S;each {circumflex over ( )}{circumflex over ( )}{circumflex over ( )} represents, independently, an alkyl or aryl hydrocarbon group linking the respective groups X1/Y1 and X2/Y2 together; andn1+n2=the coordination number of M1+the coordination number of M2.

5. The coordination polymer of claim 1, wherein the coordination polymer is a polymer having repeat units of the structure (II): -{[M1(X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1)n1M2(X2{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y2)n2][Z1]n3[Z2]n4}-   (II)where:M1 and M2 are each, independently, copper, silver, or gold;X1, X2, Y1, and Y2 are each, independently N, O, P, or S;each {circumflex over ( )}{circumflex over ( )}{circumflex over ( )} represents, independently, an alkyl or aryl hydrocarbon group linking the respective groups X1/Y1 and X2/Y2 together;wherein Z1 and/or Z2 are each, independently selected from the group consisting of:anionic halogen, anionic substituted boron, and anionic substituted phosphorous; andn1+n2=the coordination number of M1+the coordination number of M2;n3+n4=the oxidation state of the M1+the oxidation state of M2.

6. The coordination polymer of claim 1, wherein the coordination polymer is a polymer having repeat units of the structure (III): -{M1(X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1)n1}-   (III)where:M1 is copper, silver, or gold;X1 and Y1 are each, independently N, O, P, or S;each {circumflex over ( )}{circumflex over ( )}{circumflex over ( )} represents, independently, an alkyl or aryl hydrocarbon group linking X1 and Y1 together; andn1 is the coordination number of M1.

7. The coordination polymer of claim 1, wherein the coordination polymer is a polymer having repeat units of the structure (IV): -{[M1(X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1)n1][Z1]n3}-   (IV)where:M1 and M2 are each, independently, copper, silver, or gold;X1 and Y1 are each, independently N, O, P, or S;each {circumflex over ( )}{circumflex over ( )}{circumflex over ( )} represents, independently, an alkyl or aryl hydrocarbon group linking the respective groups X1 and Y1 together;wherein Z1 and/or Z2 are each, independently selected from the group consisting of:anionic halogen, anionic substituted boron, and anionic substituted phosphorous; andn1 is the coordination number of M1.n3 is the oxidation state of the M1.

8. The coordination polymer of claim 4, wherein M1 and/or M2 are independently selected from the group consisting of: Cu(I), Cu(II), Ag(I), Au(I), and Au(III).

9. The coordination polymer of claim 4, wherein M1 and/or M2 is Cu(I) and wherein each of X1, X2, Y1, and Y2 are nitrogen.

10. The coordination polymer of claim 4, wherein the compound (X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1) and/or (X2{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y2) is a heterocycle compound having at least two heteroatoms.

11. The coordination polymer of claim 10, wherein the compound (X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1) and/or (X2{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y2) is selected from the group consisting of a pyrazolate, a substituted pyrazolate, pyrazine, a substituted pyrazine, an alkyl diamine, an alkylene diamine, a polyalkylene polyamine, a polyimine, bispyridine, and a substituted bispyridine.

12. The coordination polymer of claim 11, wherein the compound (X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1) and/or (X2{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y2) is a pyrazolate having the structure (V):

13. (canceled)

14. The coordination polymer of claim 4, wherein: M1 is Cu(I);M2 is Cu(I);X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )} Y1 is 4,4′-azopyridine (PAP);X2{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y2 is 3,5-bis(trifluoromethyl)pyrazolate (3,5-(CF3)2Pz),n1 is 3; and n2 is 1.

15. The coordination polymer of claim 4, wherein: M1 is Cu(I);M2 is Cu(I);X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1 is 4,4′-azopyridine (PAP);X2{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y2 is 3,5-bis(trifluoromethyl)pyrazolate (3,5-(CF3)2Pz),n1 is 2; and n2 is 1.

16-17. (canceled)

18. The coordination polymer of claim 4, wherein:M1 is Cu(I);M2 is Cu(I);X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1 is 1,4-pyrazine;X2{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y2 is 3,5-bis(trifluoromethyl)pyrazolate (3,5-(CF3)2Pz),n1 is 2; and n2 is 2.

19. (canceled)

20. The coordination polymer of claim 7, wherein: M1 is Cu(I);X1{circumflex over ( )}{circumflex over ( )}{circumflex over ( )}Y1 is 4,4′-azopyridine (PAP), 4,4′-bipyridine, 1,2-bis(4-pyridyl)ethane, 1,4-pyrazine, 1,4-piperazine, or 1,2-bis(4-pyridyl)ethyleneZ1 is BF4;n1 is 4; and n3 is 1.

21. A method of preparing a coordination polymer comprising: mixing a metal compound with a negatively charged counterion precursor to form an intermediate product, wherein the metal compound is selected from the group consisting of copper, silver, and gold;mixing the intermediate product with at least one neutral bridging electron-donor organic ligand to form the coordination polymer.

22-37. (canceled)