A dual-functional 2D coordination polymer exhibiting photomechanical and electrically conductive behaviours.

A photoactive two-dimensional coordination polymer (2D CP) [Zn2(4-spy)2(bdc)2]n (1) [4-spy = 4-styrylpyridine and H2bdc = 1,4-benzendicarboxylic acid] undergoes a photochemical [2 + 2] cycloaddition reaction upon UV irradiation. Interestingly, the crystals of 1 show different photomechanical effects, such as jumping, swelling, and splitting, during UV irradiation. In addition, the CP was employed for conductivity measurements before and after UV irradiation via current density-voltage characteristics and impedance spectroscopy, which suggest that they are semiconducting in nature and can be used as Schottky diodes. Thus, this work demonstrates the potential dual applications of a 2D CP based on photosalient and conductivity properties.

In Situ Oxidation of Pyridyl-Dihydrobenzoimidazoquinazoline and the Synthesis of a Highly Luminescent Cd(II) Coordination Polymer: A Promising Candidate for Mutagenic Nitroaromatic Detection and Device Fabrication.

Pyridyl-substituted imidazoquinoline, a potent fluorescent framework, is advantageous to architect multifunctional coordination networks for sensing and fabricating emergent electrical conductors. In this work, a Cd(II)-based one-dimensional (1D) coordination polymer (1D CP), [Cd(glu)2(pbiq)2(H2O)]n (1), [H2glu = glutaric acid and pbiq = 4-(6-(pyridin-4-yl)benzo[4,5]imidazo[1,2-c]quinazoline)], has been structurally confirmed by single-crystal X-ray crystallography. The H-bonding and π···π interactions built a three-dimensional (3D) supramolecular structure that strongly emits at 416 nm in acetonitrile suspension. Potentially intrusive nitroaromatics (NAs) and trinitrophenol (TNP) selectively quench the strong emission of 1, and the highest quenching is noted in the case of TNP. A detection limit (limit of detection (LOD)) of 1.51 × 10-7 M for TNP is determined. The band gap (3.31 eV) of 1 recognizes semiconducting behavior, and an electronic device is fabricated. The correlation of current vs voltage (I-V plot) reveals a substantial non-ohmic electrical conductivity of 1 (Λ: 1.10 × 10-5 S m-1) along with a low energy barrier (ΦB: 0.69), and the series resistance (Rs) becomes 6.21 kΩ.

Cu(II)-Based Molecular Hexagons Forming Honeycomb-like Networks Exhibit High Electrical Conductivity.

Four new Cu(II)-based hexagonal complexes with the metallomacrocycle formulae [Cu6(5-nip)6(3-py)6(H2O)12] (1), [Cu6(5-nip)6(3-Clpy)6(H2O)12] (2), [Cu6(5-nip)6(3-Brpy)6(H2O)12] (3), and [Cu6(5-nip)6(3-Ipy)6(H2O)12] (4) have been synthesized using 5-nitroisophthalic acid (H25-nip) and pyridine (py)/3-halopyridine (3-Xpy; X = Cl, Br, and I) ligands. The structural features and supramolecular interactions of compounds 1-4 have been investigated using the single-crystal X-ray diffraction (SCXRD) technique. Interestingly, the hexagonal complexes undergo hydrogen bonding and π···π stacking interactions to form fascinating two-dimensional (2D) honeycomb-like structures. The synthesized complexes exhibit high electrical conductivity, arising from charge transport through space via π···π contacts. However, complexes containing 3-Brpy (3) and 3-Ipy (4) exhibit photosensitivity due to the presence of halogens with a larger size and lower ionization energy. The conductivity results are also in accordance with the theoretical prediction calculated by density functional theory (DFT) study.

Electrically conductive Cu(II)-based 1D coordination polymer with theoretical insight.

A nitro-functionalized Cu(ii)-based one-dimensional coordination polymer (1D CP) [Cu(nip)(4-phpy)2]n (1) (H2nip = 5-nitroisophthalic acid and 4-phpy = 4-phenylpyridine) was synthesized and characterized by elemental analysis, powder X-ray diffraction (PXRD) and single crystal X-ray diffraction (SCXRD). In the solid-state self-assembly of 1, two sets of weak intermolecular forces, CHπ interaction among the axially bound 4-phpy ligands and ππ interaction among bridging nip ligands from adjacent 1D coordination polymeric chains led to 3D supramolecular packing. Interestingly compound 1 exhibited electrical conductivity in the semiconducting regime and behaved as a Schottky barrier diode.