Herein, we report a semiconductive, proton-conductive, microporous hydrogen-bonded organic framework (HOF) derived from phenylphosphonic acid and 5,10,15,20-tetrakis[pphenylphosphonic acid] porphyrin (GTUB5). The structure of GTUB5 was characterized using single crystal X-ray diffraction. A narrow band gap of 1.56 eV was extracted from a UV-Vis spectrum of pure GTUB5 crystals, in excellent agreement with the 1.65 eV band gap obtained from DFT calculations. The same band gap was also measured for GTUB5 in DMSO. The proton conductivity of GTUB5 was measured to be 3.00 × 10 −6 S cm −1 at 75°C and 75% relative humidity. The surface area was estimated to be 422 m 2 g −1 from grand canonical Monte Carlo simulations. XRD showed that GTUB5 is thermally stable under relative humidities of up to 90% at 90°C. These findings pave the way for a new family of organic, microporous, and semiconducting materials with high surface areas and high thermal stabilities.

Herein, the first semiconducting and magnetic phosphonate metal–organic framework (MOF), TUB75, is reported, which contains a 1D inorganic building unit composed of a zigzag chain of corner‐sharing copper dimers. The solid‐state UV–vis spectrum of TUB75 reveals the existence of a narrow bandgap of 1.4 eV, which agrees well with the density functional theory (DFT)‐calculated bandgap of 1.77 eV. Single‐crystal conductivity measurements for different orientations of the individual crystals yield a range of conductances from 10−3 to 103 S m−1 at room temperature, pointing to the directional nature of the electrical conductivity in TUB75. Magnetization measurements show that TUB75 is composed of antiferromagnetically coupled copper dimer chains. Due to their rich structural chemistry and exceptionally high thermal/chemical stabilities, phosphonate MOFs like TUB75 may open new vistas in engineerable electrodes for supercapacitors.

A conductive phosphonate metal-organic framework (MOF), [{Cu(H 2 O)} (2,6-NDPA) 0.5 ] (NDPA = naphthalenediphosphonic acid), which contains a 2D inorganic building unit (IBU) comprised of a continuous edge-sharing sheet of copper phosphonate polyhedra is reported. The 2D IBUs are connected to each other via polyaromatic 2,6-NDPA's, forming a 3D pillared-layered MOF structure. This MOF, known as TUB40, has a narrow band gap of 1.42 eV, a record high average electrical conductance of 2 × 10 2 S m −1 at room temperature based on single-crystal conductivity measurements, and an electrical conductance of 142 S m −1 based on a pellet measurement. Density functional theory (DFT) calculations reveal that the conductivity is due to an excitation from the highest occupied molecular orbital on the naphthalene-building unit to the lowest unoccupied molecular orbital on the copper atoms. Temperature-dependent magnetization measurements show that the copper atoms are antiferromagnetically coupled at very low temperatures, which is also confirmed by the DFT calculations. Due to its high conductance and thermal/chemical stability, TUB40 may prove useful as an electrode material in supercapacitors.

In this article, an implementation of the newest iteration of the Minnesota solvation model, SM12, into the Amsterdam density functional (ADF) computational package is presented. ADF makes exclusive use of Slater-type orbitals (STO), which correctly represent the true atomic orbitals for atoms, whereas SM12 and the underlying charge model 5 (CM5) have previously only been tested on Gaussian-type orbitals (GTO). This new implementation is used to prove the basis set independence of both CM5 and SM12. A detailed comparison of the SM12 and COSMO solvation models, as implemented in ADF, is also presented. We show that this new implementation of SM12 has a mean unsigned error (MUE) of 0.68 kcal/mol for 272 molecules in water solvent, 4.10 kcal/mol MUE for 112 charged ions in water, and 0.92 kcal/mol MUE for 197 solvent calculations of various molecules. SM12 outperforms COSMO for all neutral molecules and performs as well as COSMO for cationic molecules, only falling short when anionic molecules are taken into consideration, likely due to CM5's use of Hirshfeld charges and their poor description of anionic molecules, though CM5 seems to improve upon this discrepancy.

Herein, a simple way of tuning the optical and structural properties of porphyrin‐based hydrogen‐bonded organic frameworks (HOFs) is reported. By inserting transition metal ions into the porphyrin cores of GTUB‐5 (p‐H8‐TPPA (5,10,15,20‐Tetrakis[p‐phenylphosphonic acid] HOF), the authors show that it is possible to generate HOFs with different band gaps, photoluminescence (PL) life times, and textural properties. The band gaps of the resulting HOFs (viz., Cu‐, Ni‐, Pd‐, and Zn‐GTUB‐5) are measured by diffuse reflectance and PL spectroscopy, as well as calculated via DFT, and the PL lifetimes are measured. Across the series, the band gaps vary over a narrow range from 1.37 to 1.62 eV, while the PL lifetimes vary over a wide range from 2.3 to 83 ns. These differences ultimately arise from metal‐induced structural changes, viz., changes in the metal‐to‐nitrogen distances, number of hydrogen bonds, and pore volumes. DFT reveals that the band gaps of Cu‐, Zn‐, and Pd‐ GTUB‐5 are governed by highest occupied/lowest unoccupied crystal orbitals (HOCO/LUCO) composed of π‐ orbitals on the porphyrin linkers, while that of Ni‐GTUB‐5 is governed by a HOCO and LUCO composed of Ni dorbitals. Overall, our findings show that metal‐insertion can be used to optimize HOFs for optoelectronics and small‐molecule capture applications.

Raman spectroscopy is a rapid and noninvasive analytical technique used for the analysis of complex materials in complex matrices. Herein, we report for the first time a combined Raman-DFT study to assign all the vibrational modes associated with the most important species involved in the H 2 S scavenger reaction of HET-triazine under simulated contactor tower conditions. In doing so, we have defined specific peaks or Raman identifier bands (RIBs) to get a complete reaction profile of the H 2 S removal process. Our methodology was able to identify the presence of the elusive 2,2′-(1,3,5-thiadiazine-3,5-diyl)di(ethan-1-ol) (TDZ) intermediate and also provided evidence supporting the formation of the sulfur polymeric deposit from the 2-(1,3,5-dithiazinan-5yl)ethan-1-ol (DTZ) byproduct.

<p>We report the first semiconductive, proton-conductive, microporous hydrogen-bonded organic framework (HOF) derived from phenylphosphonic acid and 5,10,15,20‐tetrakis[<i>p</i>‐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 the 1.65 eV band gap obtained from density functional theory calculations. The same band gap was also measured for GTUB5 in DMSO. The proton conductivity of GTUB5 was measured to be 3.00 ´ 10^-6S cm^-1 at 75 °C and 75 % relative humidity. The surface area of GTUB5’s hexagonal voids were estimated to be 422 m² g^-1 from grand canonical Monte Carlo simulations. XRD showed that GTUB5 is thermally stable under relative humidities of up to 90 % at 90 °C. These findings pave the way for a new family of microporous, organic, semiconducting materials with high surface areas and high thermal stabilities. Such materials could find applications in printed electronics, optoelectronics, and electrodes in supercapacitors.<br></p>

Herein, we report on the synthesis of a microporous, three‐dimensional phosphonate metal–organic framework (MOF) with the composition Cu3(H5‐MTPPA)2 ⋅ 2 NMP (H8‐MTPPA=methane tetra‐p‐phenylphosphonic acid and NMP=N‐methyl‐2‐pyrrolidone). This MOF, termed TUB1, has a unique one‐dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.2 m2/g after removal of the solvents from the voids. The Tauc plot for TUB1 yields indirect and direct band gaps of 2.4 eV and 2.7 eV, respectively. DFT calculations reveal the existence of two spin‐dependent gaps of 2.60 eV and 0.48 eV for the alpha and beta spins, respectively, with the lowest unoccupied crystal orbital for both gaps predominantly residing on the square planar copper atoms. The projected density of states suggests that the presence of the square planar copper atoms reduces the overall band gap of TUB1, as the beta‐gap for the trigonal bipyramidal copper atoms is 3.72 eV.