SEMICONDUCTIVE AND PROTON-CONDUCTIVE POROUS HYDROGEN-BONDED FRAMEWORKS

Abstract

A hydrogen bonded organic framework (HOF) includes at least one kind of organic linker with at least one functional group forming a hydrogen-bonded network, the functional group includes a hydroxyl group and a central atom of tetrahedral geometry, the HOF is semi-conductive, proton-conductive and porous, and can even be microporous. In some embodiments, the at least one functional group is phosphonic acid, phosphinic acid, arsonic acids, arsinic acids, phosphonate, arsonate and/or esters thereof including at least one hydroxylgroup. A covalent organic framework (COF), is also provided based on an HOF for transforming the hydrogen bonds between the functional groups into covalent anhydride bonds via a condensation reaction or reactions known to form anhydrides.

Claims

1. A hydrogen-bonded organic framework (HOF) comprising at least one kind of organic linker with at least one functional group forming a hydrogen-bonded network, wherein the functional group comprise a hydroxyl group and a central atom of tetrahedral geometry, and wherein the HOF is semi-conductive, proton-conductive and porous.

2. The HOF according to claim 1, wherein the central atom of the functional group is selected from the group consisting of phosphorus (P), arsenic (As), antimony (Sb), silicon (Si), selenium (Se) and bismuth (Bi).

3. The HOF according to claim 2, wherein the functional group of the organic linker is selected from the group consisting of phosphonic acid, phosphinic acid, arsonic acids, arsinic acids, phosphonate, arsonate and/or esters thereof with at least one hydroxylgroup.

4. The HOF according to claim 1, wherein the organic linker is V-shaped, L-shaped, T-shaped, X-shaped, X-shaped tetrahedral, Y-shaped, star-shaped, linear or hexagonal geometrical core enabling the formation of void channels.

5. The HOF according to claim 1, wherein the at least one organic linker comprises porphyrin or phthalocyanine as a geometrical core.

6. The HOF according to claim 1, wherein the hydrogen-bonded network of the functional groups of the organic linkers forms one-dimensional hydrogen-bonded chains and/or two-dimensional hydrogen-bonded sheets assemble organic linkers to form one-dimensional, two-dimensional, and three-dimensional HOFs.

7. The HOF according to claim 1, wherein the organic linkers form two-dimensional hydrogen-bonded sheets, wherein the sheets assemble in multiple layers forming a three-dimensional HOF.

8. The HOF according to claim 1, wherein the HOF comprises or is composed of two kinds of organic linkers.

9. The HOF according to claim 1, wherein one kind of organic linker is phenylphosphonic acid and/or one kind of organic linker is 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (H.sub.8-TPPA).

10. The HOF according to claim 1, wherein the HOF consists of H.sub.8-TPPA and optionally phenylphosphonic acid.

11. The HOF according to claim 1, wherein functional groups of the organic linkers form one, two and/or three hydrogen bonds with each other.

12. The HOF according to claim 1, wherein the HOF has a band gap of between about ˜0 eV and about ˜4.0 eV.

13. Use of a HOF according to claim 1, as a membrane-material in a proton exchange membrane fuel cell, as an electrode material in an electrical double layer capacitor and/or supercapacitor, in a solar cell and/or in semiconductor applications.

14. A covalent organic framework (COF), characterized in that it has been generated from a HOF according to claim 1, by transforming the hydrogen bonds between the functional groups into covalent anhydride bonds via a condensation reaction or reactions known to form anhydrides.

15. A method of synthetizing a HOF according to claim 1, by combining the organic linkers of the HOF in a solution, wherein the solution comprises as suitable solvent; and the solution is incubated at about 80° C.

16. The HOF according to claim 5, wherein the geometrical core comprises a bound metal, or a transition metal.

17. The HOF according to claim 16, wherein the bound metal is at least one of iron (Fe), palladium (Pd), zinc (Zn),copper (Cu), or nickel (Ni).

18. The HOF according to claim 6, wherein the functional groups also form isolated hydrogen bonded clusters.

19. The HOF according to claim 7, wherein the (continuous) hydrogen-bonded network extends in the two-dimensional hydrogen-bonded sheets and/or between the layers of the three-dimensional HOF.

20. The HOF according to claim 8, wherein both kinds of organic linkers comprise identical functional groups.

Description

FIGURES

[0139] The invention is further described by the following figures. These are not intended to limit the scope of the invention, but represent preferred embodiments of aspects of the invention provided for greater illustration of the invention described herein.

[0140] Description of the figures:

[0141] FIG. 1: Synthetic route for meso-aryl phosphonate-functionalized porphyrin derivatives and the porous phosphonic acid hydrogen-bonded organic framework GTUB-5.

[0142] FIG. 2: Pore size distribution (PSD) of GTUB-5.

[0143] FIG. 3: (A) Simulated N2 isotherm. (B) Plot of the linear region for the BET equation.

[0144] FIG. 4: Simplified chemical structure of the GTUB5 building block, highlighting one of the phenyl-phosphonic acid groups. The bond distance labeling is used in Table 5.

[0145] FIG. 5: Simplified chemical structure of the GTUB5 building block, highlighting the dipyrromethene portion of the porphyrin group. The bond distance labeling is used in Table 5.

[0146] FIG. 6: Simplified chemical structure of the GTUB5 building block, highlighting the hydrogen bonding between neighboring phenyl-phosphonic acid groups. The bond distance labeling is used in Table 5.

[0147] FIG. 7: Comparison between experimental and theoretical X-ray diffraction patterns. The theoretical result was generated using a full width-half max of 0.1 2θ° within the Mercury software package..sup.74.

[0148] FIG. 8: (A) Band structure of GTUB5..sup.75,76 (B) The corresponding total density of states (DOS).

[0149] FIG. 9: (A) Portion of hydrogen-bonded network of GTUB5. View of hydrogen bonding interactions between PPA and H.sub.8-TPPA linkers. (B) Depiction of hexagonal void spaces in GTUB5. Two-dimensional hydrogen-bonded layers constructed from hydrogen bonding interactions between PPA and H.sub.8-TPPA linkers. (C) Layer structure of GTUB5. Three-dimensional hydrogen-bonded framework of GTUB-5 along the c-axis. (D) One-dimensional hydrogen-bonded building unit of GTUB5. View of one-dimensional infinite hydrogen-bonded chain.

[0150] FIG. 10: Thermogravimetric curves of H.sub.8TPPA and GTUB-5 between room temperature and 700° C. with a heating rate of 10° C./min.

[0151] FIG. 11: FT-IR spectra of H.sub.8-TPPA and H.sub.8TPPA-PPA (GTUB-5).

[0152] FIG. 12: UV-Vis spectrum of GTUB-5 in DMSO.

[0153] FIG. 13: Solid-state UV-Vis spectrum of GTUB-5.

[0154] FIG. 14: Cyclic voltammetry of GTUB-5.

[0155] FIG. 15: Proton conductivity of GTUB-5.

[0156] FIG. 16: Bode plot of GTUB-5 at 75° C. 90% rh. Increase font size of all axis labels.

[0157] FIG. 17: Powder x-ray diffraction of GTUB-5 before and after the proton conductivity experiment.

[0158] FIG. 18: Tauc plot from the solid-state UV-Vis spectrum of GTUB5, showing a band gap of 1.56 eV. The second jump at 2.88 eV corresponds to the Soret band of the porphyrin core at 430 nm.

[0159] FIG. 19: Periodic representation of GTUB5, with the unit cell indicated by the black box. This represents the HOMO iso-surface corresponding to an electron density of 0.01 electrons per Å.sup.3 (negative and positive phases are shown in red and blue, respectively). (O—red; N—blue; P—yellow; C—black; H—white).

[0160] FIG. 20: HOMO and LUMO iso-surfaces, corresponding to an electron density of 0.01 electrons per Å.sup.3. (A) Top view. (B) Side view. Red/blue correspond to the negative/positive phases. (O—red; N—blue; P—yellow; C—black; H—white).

[0161] FIG. 21: Projected density of states (pDOS) for P, O, N, C, and H in GTUB5, generated using scripts from Ref. 51.

[0162] FIG. 22: Preferred examples of organic linkers of the HOFs of the invention comprising different geometrical cores. (A) V, (B) L, (C-D) T, (E-G) X, (H) Y shaped and (I) hexagonal linkers with extending tether arms, wherein X=C or Si; E=P or As; n=0,1,2, 3 or 4; R=H, methyl, ethyl or isopropyl.

[0163] FIG. 23: (A) Crystal structure of the one-dimensional hydrogen-bonded building unit of “HOF1” constructed using H.sub.8TPPA as a sole organic linker. (B) The void channels and two-dimensional network of “HOF1” constructed using using H.sub.8TPPA as a sole organic linker. The HOF displayed in this figure (termed “HOF1”) was synthesized by heating H.sub.8TPPA in a solution of N-methyl-2-pyrrolidone (NMP) and ethanol at 80° C. in scintillation vials.

[0164] FIG. 24: (A) Crystal structure of the one-dimensional hydrogen-bonded building unit of “HOF2” constructed using H.sub.8TPPA as a sole organic linker. The hydrogens are omited in the structure. (B) The void channels and view of a two-dimensional layer of “HOF2”, which are connected by the one-dimensional hydrogen bonded building unit in FIG. 24A to form the three-dimensional HOF2. HOF2 is constructed using H.sub.8TPPA as a sole organic linker. The HOF displayed in this figure (termed “HOF2”) was synthesized by heating H.sub.8TPPA in a dimethylacetamide and ethanol solution mixture at 80° C. for two days in scintillation vials. Phenylphosphonic acid was added to the solution mixture as a modulator. Hydrogen atoms between dashed line connected oxygens in FIG. 24A and 24B are omitted in the structure for clarity.

EXAMPLES

[0165] The invention is further described by the following examples. These are not intended to limit the scope of the invention, but represent preferred embodiments of aspects of the invention provided for greater illustration of the invention described herein.

Summary of the Examples

[0166] Disclosed herein is a novel semiconductive, proton-conductive microporous hydrogen-bonded organic framework derived from phenylphosphonic acid and 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (known as GTUB5). The structure of GTUB5 was characterized using single crystal X-ray diffraction (XRD). A narrow band gap of 1.56 eV was extracted from a UV-Vis spectrum of pure GTUB5 crystals, in excellent agreement with that obtained from DFT calculations. GTUB5 was found to have a proton conductivity of 3.00.Math.10.sup.−6 S cm.sup.−1 at 75° C. and 75% relative humidity. Its hexagonal voids were found to have a surface area of 422 m.sup.2g.sup.−1. GTUB5 is thermally stable under relative humidities of up to 90% at 75° C., as shown by XRD. These findings pave the way for a new family of microporous, proton-conductive organic semiconductors with high surface areas and high thermal stability is the first example with both semiconductive and proton-conductive behaviour.

Materials and Methods of the Examples

[0167] Synthesis of GTUB5. All the reagents and solvents employed were commercially available and used as received without further purification. As can be seen in Scheme of FIG. 1, 5,10,15,20-Tetra(p-bromophenyl)porphyrin (TBPP) and phosphonate-functionalized porphyrins (TDPP, TPPP, H.sub.8-TPPA) were synthesized employing our previously reported synthetic route..sup.54 To synthesize GTUB-5, H.sub.8-TPPA (8.77 mg, 0.0088 mmol) and phenylphosphonic acid (PPA) (208 mg, 1.3 mmol) in a 1.6 mL mixture of DMF/EtOH or DMF/MeOH (1.36:0.24, v/v) were added to a 5-mL glass vial. The reaction mixture was ultrasonically dissolved and then heated to 80° C. in an oven for 48 h. After cooling down to room temperature, dark purple block crystals of GTUB5 have been formed, which were then isolated by filtration, washed with DMF and acetone, and finally air-dried. The yield of GTUB5 was ˜5 mg.

[0168] Molecular simulations. Accessible pore volume, pore size distribution (PSD) and surface area of GTUB-5 were calculated by computer simulations. These force field based atomistic simulations were performed with the RASPA molecular simulation package..sup.55 For these simulations GTUB-5 unit cell was replicated by 1×2×4 times in the x, y and z directions, respectively. The replicated framework atoms were fixed in their crystallographically determined positions. Lennard-Jones (LJ) and Coulomb potentials were employed to determine the non-bonded interaction energies between atoms:

[00001]$V_{\mathrm{ij}}=4{\epsilon }_{\mathrm{ij}}\left[{\left(\frac{{\sigma }_{\mathrm{ij}}}{r_{\mathrm{ij}}}\right)}^{12}-{\left(\frac{{\sigma }_{\mathrm{ij}}}{r_{\mathrm{ij}}}\right)}^6\right]+\frac{q_i{q}_j}{4{\epsilon }_0{r}_{\mathrm{ij}}}$

where r.sub.ij is the distance between atoms i and j, ε.sub.ij and σ.sub.ij are the LJ well depth and diameter, respectively, q.sub.i is the partial charge of atom i, and ε.sub.0 is the dielectric constant. In all simulations, the LJ parameters between different types of sites were calculated using the Lorentz-Berthelot mixing rules, and the Ewald summation method was employed to compute the electrostatic interactions. The LJ interactions were shifted to be 0 at a cutoff distance of 12.0 Å. For the real part of the Ewald summation, the cutoff was also set to 12.0 Å.

[0169] LJ parameters for the GTUB-5 atoms (see Table 3) were taken from the DREIDING.sup.56 force field. Partial atomic charges for the framework atoms were obtained with the REPEAT method.sup.57 which fits point charges against the electrostatic potential. The electrostatic potential of GTUB-5 was derived from a single point energy calculation using periodic plane-wave DFT with the CASTEP 17.21 software.sup.58 and by employing the PBE.sup.59 functional and ultrasoft pseudopotentials.sup.69 with a 550 eV cutoff.

TABLE-US-00003 TABLE 3 LJ parameters for the framework atoms of GTUB-5 Atom type σ (Å) ε/k.sub.B (K) C 3.473 47.856 O 3.033 48.158 H 2.846 7.649 P 3.695 153.476

[0170] Accessible pore volume. Accessible pore volume of GTUB-4 was computed with the Widom insertion method using a helium probe.sup.61 and estimated to be 0.176 cm.sup.3/g. This method included the random insertion of a single helium atom for 100,000 times in to the framework. Then the specific pore volume, i.e. pore volume available per unit mass, V.sub.p, was determined by

[00002]$V_p=\frac{1}{m_s}\int e^{-\phi \left(R\right)/\mathrm{kT}}\mathrm{dr}$

where ϕ is the helium-solid interaction potential for a single helium atom, dr is a differential volume element, and m.sub.s is the mass of the solid adsorbent in the simulation box. The LJ parameters for helium were taken from Hirschfelder et al.,.sup.62 and are σ.sub.He=2.640 Å and ε.sub.He/k.sub.B=10.9 K.

[0171] Pore size distribution. The pore size distribution of GTUB-5 (FIG. 2) was computed with the method of Gelb and Gubbins..sup.63 Briefly, this method considers subvolumes of the system accessible to spheres of different radii r. Let V.sub.pore(r) be the volume of the void space “accessible” by spheres of radius r or smaller; a point x can only be considered in V.sub.pore(r) if we can construct a sphere of radius r that overlaps x and does not overlap any framework atoms. The derivative −dV.sub.pore(r)/dr is the fraction of volume accessible by spheres of radius r but not by spheres of radius r+dr and is a direct definition of the pore size distribution. The V.sub.pore(r) function was calculated by Monte Carlo volume integration (10,000 iterations) and setting dr=0.12 Å.

[0172] N.sub.2 adsorption isotherm and BET surface area. Simulated N.sub.2 adsorption isotherm of GTUB-5 was computed by by performing grand canonical Monte Carlo (GCMC) simulations at 77 K and up to 0.4 bar. In the GCMC ensemble, the chemical potential, volume, and temperature of the system are fixed; however, the number of molecules fluctuate. For all GCMC simulations a 100.000 cycle initialization and a 100,000 cycle production run were performed. Each cycle is N steps, where N is equal to the number of molecules in the system. Random insertions, deletions, translations, rotations, and reinsertions of the N.sub.2 molecules were sampled with equal probability. TraPPE force field was used to model N.sub.2 molecules,.sup.64 which was originally fit to reproduce the vapor-liquid coexistence curve of N.sub.2. In this force field, the N.sub.2 molecule is rigid where the N—N bond length is fixed at its experimental value of 1.10 Å. This model reproduces the experimental gas-phase quadrupole moment of the N.sub.2 molecule by placing partial charges on nitrogen atoms and on a point located at the center of mass (COM) of the molecule. Table 4 shows the LJ parameters and partial charges for the N.sub.2 molecule.

TABLE-US-00004 TABLE 4 LJ parameters and partial charges for the sites in the N.sub.2 molecule σ (Å) ε/k.sub.B (K) q (e) N 3.31 36.0 −0.482 N.sub.2 COM 0 0 0.964

[0173] With GCMC simulations once can compute the absolute adsorption (N.sub.total); whereas, in adsorption experiments excess adsorption (N.sub.excess) is measured. Therefore, the simulated excess adsorption of N.sub.2 was calculated using the following expression

N.sub.total=N.sub.excess+p.sub.gas×V.sub.p

where p.sub.gas is the bulk density of the gas at simulation conditions which were calculated using the Peng-Robinson equation of state and V.sub.p is the accessible pore volume. BET surface area of GTUB-5 was obtained by using the simulated N.sub.2 adsorption isotherm of GTUB-5 (FIG. 3) and estimated to be 422 m.sup.2/g. When applying the BET theory, we made sure that our analysis satisfied the two consistency criteria as detailed by Walton et al..sup.65

[0174] Electronic structure. All of the density functional theory (DFT) calculations on GTUB5 were performed with the Quickstep-CP2K program..sup.66,67 Since GTUB5 is a bulk material, periodic boundary conditions were applied to a 1×1×1 cell. The Perdew-Burke-Ernzerhof (PBE)60 generalized gradient approximation (GGA) functional was used in conjunction with the Grimme D3 dispersion correction.sup.67 and BJ damping..sup.68 The Gaussian and plane waves method.sup.67,69 was used, with the valence orbitals expanded in terms of molecularly optimized Gaussian basis sets of double-ζ plus polarization (MOLOPT-DZVP).sup.70 quality and the core electrons represented by norm-conserving Goedecker-Teter-Hutter pseudopotentials..sup.71,72 ┌-point sampling was used and the plane-wave cutoff in reciprocal space was set to 550 Ry, with a Gaussian mapping of 60 Ry over five multi-grids. The self-consistent field was converged to 10.sup.−6 Ry with the FULL_ALL preconditioner using the orbital transformation method with a HOMO-LUMO gap of 1.67 eV for both the geometry optimization and the follow-up single point calculations. The experimental crystal structure was relaxed using the conjugate gradient method.sup.73, and the lattice vectors were set to their experimental values. Single point calculations were performed to obtain the projected density of states, band structure, band gap, and the HOMO and LUMO iso-surfaces.

TABLE-US-00005 TABLE 5 Comparison of experimental and calculated average inter-atomic distances (in Å). Standard deviations in distances are given in brackets. The calculated structure was obtained from a geometry optimization of the experimental crystal structure at the PBE-D3-BJ DZVP-550 Ry level of theory. Atom pair Experimental Calculated FIG. 4 C—P 1.78 1.80 (0.018) (0.008) P—O 1.53 1.58 (0.003) (0.013) O—H 0.83 1.16 (0.013) (0.096) C—C 1.49 1.46 (0.000) (0.023) C═C 1.39 1.40 (0.025) (0.01) FIG. 5 N—C 1.78 1.80 (0.018) (0.008) N═C 1.53 1.58 (0.003) (0.013) N—H 0.88 1.05 (0.012) (0.015) N—N 2.92 2.93 (0.000) (0.000) FIG. 6 O—O 2.47 2.43 (0.018) (0.000) O—H 1.88 1.75 (0.164) (0.005)

[0175] X-ray data collection and structure refinement. Data for GTUB-5 was obtained with a Bruker APEX II QUAZAR three-circle diffractometer. Indexing was performed using APEX2..sup.77 Data integration and reduction were carried out with SAINT..sup.78 Absorption correction was performed by the multi-scan method implemented in SADABS..sup.79 The structure was solved using SHELXT.sup.80 and then refined by full-matrix least-squares refinements on F.sup.2 using the SHELXL.sup.81 in the Olex2 software package..sup.82 The positions of all H-atoms bonded to carbon, nitrogen, and oxygen atoms were geometrically optimized with the following HFIX instructions in SHELXL: HFIX 23 for the —CH.sub.2— moieties, HFIX 137 for the —CH.sub.3, HFIX 43 for the CH and NH groups of the aromatic rings and porphyrin cores, and HFIX 147 for the —P—OH groups (H1a) of the phosphonic acid moieties. Another O-bound H atom (H3) was located from a difference Fourier-map. Finally, their displacement parameters were set to isotropic thermal displacements parameters (U.sub.iso(H)=1.2×U.sub.eq for CH, NH and CH.sub.2 groups or (U.sub.iso(H)=1.5×U.sub.eq (—OH and CH.sub.3 groups). In the chemical formula [(H.sub.8-TPPA)(PPA).sub.2(DMA.sub.4] of GTUB-5, there is the H.sub.8-TPPA building block is not deprotonated while protons of the phenylphosphonic acid (PPA) groups have been acquired by DMF solvent in the pores forming four dimethylammonium cations ([NH.sub.2(CH.sub.3).sub.2].sup.+, DMA) to balance the charge. SQUEEZE was used to remove electron density caused by seriously disordered solvent molecules in GTUB-5. Along the c-axis, the 3D supramolecular network of GTUB-5 produced a one-dimensional distinctive void space with a total potential solvent area occupying 19.2% (785 Å.sup.3) of the unit cell volume (4081.7 Å.sup.3) obtained using the PLATON software package..sup.84 Analysis of solvent accessible voids in the structure was performed using the CALC SOLV within PLATON with a probe radius of 1.20 Å and grid spacing of 0.2 Å. Van der Waals (or ion) radii used in the analysis are 1.70 Å for C, 1.20 Å for H, 1.55 Å for N, 1.52 Å for O, and 1.80 Å for P. Also, in this crystal structure, the rotationally disordered phosphonate part (—PO.sub.3) in phenylphosphonic acid (PPA) was refined as 0.77:0.23. Crystallographic data and refinement details of the data collection for

[0176] GTUB-5 are given in Table 6. Crystal structure validations and geometrical calculations were performed using PLATON..sup.83 The Mercury software package.sup.75 was used for visualization of the cif files. Additional crystallographic data with CCDC reference numbers (1963794 for GTUB-5) was deposited to the Cambridge Crystallographic Data Center at www.ccdc.cam.ac.uk/deposit.

TABLE-US-00006 TABLE 6 X-ray crystallographic data and refinement parameters for GTUB-5. CCDC 1963794 Empirical formula C.sub.64H.sub.76N.sub.8O.sub.18P.sub.6 Formula weight/g. mol.sup.−1 1431.14 Temperature/K 296 Radiation, Wavelength (Å) MoK.sub.α (λ = 0.71073) Crystal system Monoclinic Space group C2/m a/Å 25.452(2) b/Å 22.863(2) c/Å 7.1798(6) α/° 90 β/° 102.325(6) γ/° 90 Crystal size/mm.sup.3 0.43 × 0.14 × 0.12 Volume/Å.sup.3 4081.7(6) Z 2 ρ.sub.calcd (g. cm.sup.−3) 1.164 μ (mm.sup.−1) 0.195 F(000) 1500 2θ range for 5.96 to 50.04 data collection (°) h/k/l −30 ≤ h ≤ 30, −27 ≤ k ≤ 27, −8 ≤ l ≤ 8 Reflections collected 21748 Independent reflections 3692 [R.sub.int = 0.0572, R.sub.sigma = 0.0449] Data/restraints/parameters 3692/33/247 Goodness-of-fit on F.sup.2 (S) 1.036 Final R indices [I > 2σ(I)] R.sub.1 = 0.0769, wR.sub.2 = 0.2197 R indices (all data) R.sub.1 = 0.1108, wR.sub.2 = 0.2485 Largest diff. 0.47/−0.38 peak/hole/e Å.sup.−3

TABLE-US-00007 TABLE 7 Hydrogen bond parameters (in Å and °) for GTUB-5. D-H . . . A d(D-H) d(H . . . A) d(D-H . . . A) ∠ D-H . . . A O1—H1A . . . 0.82 1.74 2.450(6) 144.05 O5.sup.i O3—H3 . . . 0.85 1.68 2.522(5) 171.88 O2.sup.ii N3—H3B . . . 0.89 2.06 2.945(13) 170.41 O4.sup.iii N3—H3C . . . 0.89 2.08 2.956(12) 167.22 O5.sup.iv Symmetry codes: (i) 3/2 − x, 3/2 − y, 1 − z; (ii) 3/2 − x, 3/2 − y, 2 − z; (iii) 3/2 − x, −1/2 + y, 1 − z; (iv) 3/2 − x, 3/2 − y, −z.

[0177] Thermogravimetric analysis (TGA). TGA on GTUB-5 was performed using a Mettler-Toledo TGA/DSC STARe System at a heating rate of 10 K min.sup.−1 under an atmosphere of dry argon over a range from 50 to 700° C. (FIG. 10).

[0178] Spectroscopy. IR spectra of H.sub.8TPPA and GTUB-5 were recorded between 4000 and 550 cm.sup.−1 using a Perkin Elmer Spectrum 100 FT-IR spectrometer with an attenuated total reflection (ATR) accessory featuring a zinc selenide (ZnSe) crystal (FIG. 11).

[0179] The solid-state diffuse reflectance ultraviolet-visible (UV-Vis) spectrum of GTUB-5 crystals was collected on a Varian Cary 300 UV-Vis Spectrophotometer (FIG. 13) and the corresponding solution spectrum was collected using a Varian Eclipse spectrofluorometer with 1-cm path length cuvettes at room temperature in DMSO (FIG. 12).

[0180] The HOMO-LUMO gap of GTUB-5 was extracted using cyclic voltammetry (see FIG. 14)..sup.84 From the measurement, the first oxidation and reduction potentials of GTUB-5 in DMSO were determined to be 0.42 V and −1.23 V, which gives rise to a HOMO-LUMO gap of 1.65 eV.

[0181] Proton conductivity measurement. The proton conductivity of GTUB-5 was determined by electrochemical impedance spectroscopy (FIGS. 15 and 16). A Zahner Zennium electrochemical workstation was used with an oscillation voltage of 10 mV over a frequency from 1 to 10.sup.6 Hz. The needles were compressed between two glassy carbon electrodes by a torque of 30 cNm to obtain pellets of 82 mm in diameter and approx. 0.114 mm thickness. The stack was placed in a PTFE sample holder. The sample holder was placed in a stainless-steel chamber with an attached water reservoir. The relative humidity (% rh) was determined by the Clausius-Clapeyron relation and controlled by heating the cell and water reservoir. The sample is held overnight at the desired % rh and temperature before measuring each data point. To ensure reproducibility, each data point was measured three times.

[0182] Powder x-ray diffraction. PXRD patterns of the GTUB-5 sample were measured on a PANalytical X'pert PRO theta-theta x-ray diffractometer (Mavern Panalytical B.B., Almelo, Netherlands) operation at 40 kV and 40 mA, before and after the proton conductivity experiment (FIG. 17). The sample was placed on a silicon zero background sample holder. Measurements were performed in the range of 3-50 2θ° with a step size of 0.026 2θ° and a counting time of 246.840 s. The results of the measurements were processed with the software Highscore plus version 4.8.

Description of the Examples

[0183] GTUB5 as described in the present examples is the first HOF to be described with both semiconductive and proton-conductive behaviour. Thermally stable and permanently microporous semiconducting HOFs of the present invention could revolutionize the design of supercapacitors and electrodes due to their simpler chemistry compared to the MOFs. Herein, the first example of a HOF (known as GTUB5), synthesized using phosphonic acid functional groups R—PO.sub.3H.sub.2, which simultaneously exhibits electrical conductivity, proton conductivity, and high thermal stability, is described.

[0184] As seen in FIG. 9A, phosphonic acid functional group has two protons and one oxygen from the P═O bond, which allow them to form multiple hydrogen bonds between each other and thereby stabilize the resulting HOF. Interestingly, the unique structure and multiple metal binding modes of the phosphonic acid functional group have led to some of the most thermally.sup.34 ,43-46 and chemically stable.sup.34, 47-49 MOFs in the literature. The phosphonic acid functional group R—PO.sub.3H.sub.2 involves two deprotonation modes with pKa values of 1.7 and 7.4, respectively. Therefore, in order to create the first phosphonate HOF in the literature, we have adopted a novel crystallization method at pH values between 1.7 and 7.4 with mixed phosphonic acid linkers of phenylphosphonic acid (PPA) and 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (H.sub.8-TPPA) to ensure that at least one of the phosphonic acid moieties is not fully deprotonated. H.sub.8-TPPA exhibits a planar tetratopic geometry with a 90° angle between the phenylphosphonate tethers.sup.49-51. Therefore, it is expected that within the mixed linker strategy H.sub.8-TPPA and phenylphosphonic acid could produce two-dimensional HOFs with hexagonal void channels.

[0185] The H.sub.8-TPPA linker was synthesized according to our previously reported method involving a Pd-catalyzed Arbuzov reaction.sup.50 in order to avoid the porphyrin core being occupied by Ni(II) after nickel catalyzed Arbuzov reaction.sup.49, 51. The synthesized metal free H.sub.8TPPA linker eliminated the possibility of potential metal-ligand interactions that could have triggered the formation of MOFs. Due to the ionic radius of Pd and its charge, it is relatively difficult for Pd to coordinate to the nitrogen atoms in the central porphyrin core after the synthesis of H.sub.8TPPA. Therefore, this strategy allows the production of metal free H.sub.8TPPA, which makes the introduction of variety of transition metal ions into porphyrin core possible. The identity of the metal ions in the porphyrin and phthalocyanine cores could be used to perform band gap modulations to optimize the conductive behavior of HOFs.

[0186] GTUB5 was synthesized following conventional MOF crystallization methods in scintillation vials in DMF/EtOH and at pH between 1.7 and 7.44 to ensure the presence of protonated phosphonic acid functional groups.sup.32. 1.7 and 7.44 correspond to pKa1 and pKa2 of phenylphosphonic acid respectively. When pH value is equal to the pKa of an acid molecule, the acid molecule is considered to be half deprotonated. The synthesis of GTUB5 gave 1-2 mm dark purple long needle-shaped crystals in almost 100% yield. The dark purple color of GTUB5 is an indication of its conductive behavior. The structure of GTUB5 was characterized using single crystal X-ray diffraction. As seen in FIGS. 9A and 9B, GTUB5 is composed of two-dimensional sheets of hydrogen-bonded H.sub.8-TPPA and phenyl phosphonic acid moieties. The structure contains two different hydrogen bonding patterns, which are observed between different H.sub.8-TPPA units and between H.sub.8-TPPA and phenylphosphonic acid (see FIG. 9D). In the first pattern, the P═O bond from the H.sub.8-TPPA unit is exclusively involved in creating the (almost linear) double hydrogen bonding pattern between each unit. In the second pattern, the hydrogen bond forms between the second protonated hydroxyl group of the H.sub.8-TPPA and deprotonated PPA.sup.2− (where PPA=phenylphosphonic acid). The four DMF solvents in the HOF structure acted as a Lewis base acquiring the PPAs' protons.

[0187] The Brunauer-Emmett-Teller (BET) surface area of GTUB5 was estimated to be 422 m.sup.2 g.sup.−1 from a simulated N.sub.2 adsorption isotherm at 77 K (see FIG. 3) obtained using the grand canonical Monte Carlo method.

[0188] The band gap was estimated from a solid-state diffuse reflectance UV-Vis spectrum of the GTUB5 crystals (see FIG. 13). As seen in FIG. 18, the Tauc plot derived from the spectrum yields a narrow band gap of 1.56 eV. The second jump at 2.88 eV corresponds to the Soret band of the porphyrin core at 430 nm. A similar band gap of 1.65 eV was also obtained from a UV-Vis spectrum of a dissolved sample of GTUB5 in DMSO (see FIG. 12), suggesting that the hydrogen-bonded supramolecular structure of the HOF is not disrupted in a polar aprotic solvent. From a cyclic voltammetry measurement on GTUB5 in DMSO (see FIG. 14), the first oxidation and reduction potentials were measured to be 0.42 V and −1.23 V, respectively, yielding a HOMO-LUMO gap of 1.65 eV supporting this hypothesis. Such properties make GTUB5 and phosphonic acid HOFs, superior compounds to be used in printed electronics.

[0189] Semiconductivity of GTUB5. To gain insight into the semiconductive nature of GTUB5, we performed density functional theory (DFT) calculations. The details of the calculations, employing hybrid Gaussian plane-wave (GPW) basis sets, can be found in the supplementary materials. FIG. 19 shows a periodic representation of the optimized geometry, which is in close agreement with the experimental crystal structure (see Table 5 and FIGS. 4-7). A single point calculation on the optimized structure yields a band gap of 1.65 eV, in very good agreement with the experimental result of 1.56 eV. As seen in FIG. 19, the HOMO and LUMO are predominantly localized on some of the porphyrins within the supercell (of which, a single unit cell is delineated by the black rectangle), but not all of them; with the LUMO occupying the same porphyrins as the HOMO.

[0190] Focusing in on the portions of the structure that have significant HOMO and LUMO density, we see that the HOMO and LUMO are localized on the same porphyrin (see FIG. 20). Moreover, they are mostly confined to a subset of the carbons and nitrogens. The HOMO is composed of π orbitals mostly on sp.sup.2 hybridized carbons and nitrogens, while the LUMO is composed of π* orbitals on some of the sp.sup.2 carbons and nitrogens. As shown in Table 8, ˜75% of the HOMO and LUMO orbital contributions are from the carbon and nitrogen 2p orbitals of the porphyrin. Table 8 also shows that a HOMO-LUMO transition would lead to an increase in the carbon 2p.sub.x orbital population, a slight decrease in the carbon 2p.sub.y population, and a slight increase in the carbon 2p.sub.z population; while the nitrogen 2p.sub.x and 2p.sub.z populations both decrease (the 2p.sub.y population remains negligible). These results suggest that the semiconductive nature of GTUB5 is predominantly determined by π-π* transitions involving orbitals localized on some of the porphyrin carbons and nitrogens. Inspection of the projected density of states (pDOS) confirms that the HOMO-LUMO gap is predominantly due to orbitals localized on carbons and nitrogens (see FIG. 21).

TABLE-US-00008 TABLE 8 Contributions from the 2p orbitals on the porphyrin carbons and nitrogens to the HOMO and LUMO. Carbon 2p.sub.x 2p.sub.y 2p.sub.z Sum HOMO 0.366 0.042 0.134 0.541 LUMO 0.484 0.020 0.170 0.674 Nitrogen 2p.sub.x 2p.sub.y 2p.sub.z HOMO 0.163 4.70 × 10.sup.−07 0.053 0.216 LUMO 0.048 5.22 × 10.sup.−4  0.020 0.067

[0191] Thermogravimetric analysis. Thermogravimetric analysis (TGA) indicates an initial 2% loss between 50 and 100° C. suggesting that remaining solvent molecules evaporating. The following ca. 12% step until 250° C. corresponds to the unbound solvent molecules of DMF (12.9% calculated). The remaining organic components of GTUB5 decompose in two steps until 900° C. The presence of large weight loss at ca. 900° C. suggests the formation of thermally stable other species at temperatures above 400° C.

[0192] Proton conductivity of GTUB5. Given the presence of —PO.sub.3H.sub.2 groups in its hydrogen-bonded framework, the proton conductivity of GTUB5 was measured. Electrochemical impedance spectroscopy measurements were carried out at 75% and 90% relative humidity (% rh) and temperatures in the range of 25 to 75° C. (see supplementary materials and Ref. 53 for setup details). At 75% rh, we see that the proton conductivity of GTUB5 increases from 8.29.Math.10.sup.−7 to 3.00.Math.10.sup.−6 S cm.sup.−1 as the temperature is increased from 25 to 75° C., while a non-monotonic increase is observed at 90% rh (see Table 9 for full data set).

TABLE-US-00009 TABLE 9 Proton conductivities and activation energies (E.sub.A) of GTUB5 at different relative humidities. Relative humidity [% rh] 75 90 25° C. 8.29 .Math. 10.sup.−7 3.55 .Math. 10.sup.−6 Conductivity [S cm.sup.−1] 50° C. 1.67 .Math. 10.sup.−6 3.26 .Math. 10.sup.−6 75° C. 3.00 .Math. 10.sup.−6 4.20 .Math. 10.sup.−6 E.sub.A [eV] 0.26 0.13

[0193] Furthermore, at a given temperature, we observe an increase in the proton conductivity with increasing relative humidity. The activation energies, as sum of the migration energy and the formation energy of defects, were extracted from the slopes of the Arrhenius plots (see FIG. 15) to be E.sub.A=0.26 eV and E.sub.A=0.13 eV at 75° C. and 90° C., respectively. These low activation energy values suggest that a Grotthuss mechanism with high proton movability and therefore low migration energy is the predominant mechanism for proton conduction through the framework. As seen in FIG. 17, the XRD pattern of the sample recorded before and after the proton conductivity experiments slightly changes, indicating that the structure was slightly affected by the humidified atmosphere and the applied temperatures up to 75° C. during the measurements.

Conclusion of the Examples

[0194] In conclusion, GTUB5 represents the first member of a novel family of two-dimensional, microporous phosphonic acid HOFs with calculated surface area of 422 m.sup.2/g. Given its low band gap (as confirmed by solid-state/solution measurements and DFT calculations), GTUB5 paves the way for the creation of new semiconductive microporous compounds. Within the context of semiconductive microporous compounds, GTUB5 is the first HOF in the literature exhibiting such a small band gap.

[0195] The use of hydrogen bonds in constructing a framework comes with the advantage of less complex connectivity options and eliminate the presence of toxic metal ions in capacitors and batteries providing environmentally friendlier solutions.

[0196] Among, other HOFs, due to the tetrahedral geometry and the presence of three oxygen atoms, phosphonic acid HOFs provide more structural diversity and further potential applications. Phosphonic acids have d orbitals, which provides additional properties to the HOF compounds and interactions with the organic core. In addition to its narrow band gap within the semiconductive region, GTUB5 exhibits proton conductive behavior as well. Based on the present example, different linker geometries and pH modulations can be designed by a person skilled in the art to further optimize the pore sizes and conductive behavior of phosphonic acid-HOFs. Given the high surface area and narrow band gap of GTUB5, phosphonate-HOFs have the potential to revolutionize the semiconductive materials industry with applications in electrodes and suparcapacitors, optoelectronics, solar panels. Such HOFs could be further used in thin films on surfaces, optoelectronic applications, solar panels, printed electronics such as screen printing, flexography, gravure, offset lithography, and inkjet. Furthermore, such HOFs could be used to construct active or passive devices such as thin film transistors, coils, resistors. Semiconductive HOFs would provide important advantages due to their simpler chemistry and solubilities compared to the MOFs.

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