Structural Diversity of Copper(I) Cluster-Based Coordination Polymers with Pyrazine-2-thiol Ligand

Abstract

Six novel copper­(I) cluster-based coordination polymers (CPs) [Cu9(pzt)7Cl2] n (1), [Cu2(pzt)­Cl] n (2), [Cu4(pzt)3Br] n (3), [Cu­(pzt)] n (4), [Cu4(pzt)3I] n (5), and [Cu7(pzt)6I] n (6) were solvothermally synthesized using Hpzt (Hpzt = pyrazine-2-thiol) ligand and well-characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD). Six CPs exhibit either 2D (4 and 6) or 3D (1–3, and 5) network based on diverse multinuclear {Cu x S y } clusters. The structural evolutions of 1–6 are greatly influenced by types of metal halides and the ligand-to-metal molar ratio used in the reaction. Among them, compound 1 displays interesting temperature-dependent photoluminescence arising from triplet cluster-centered (3CC) excited state from the cluster metal core. Compounds 1–6 also exhibit photocurrent responses upon visible-light illumination (λ = 420 nm) in the order 6 > 5 > 3 > 1 > 4 > 2. This work not only shows the structural diversity of {Cu x S y } clusters-based CPs but also provides an interesting insight into structural modulation using crystal engineering concept.

V═O Functionalized {Tm2}–Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO2 and Oxidation of Mustard Gas

“…Furthermore, with CO 2 loading, no obvious change in the Q st value was observed, indicating that the binding sites were homogeneous. Moreover, it is worth noting that the extremely high isosteric heat value was probably caused by the additional contribution of vanadium ions with significant π back-bonding, which gave NUC-11 an excellent potential separation performance for mixed gases, just as was documented for VMOF-74 . , …”

Recent Progress in Luminescent Cu(I) Halide Complexes: A Mini-Review

“…. .Cu bond distances, capable of influencing CC-assisted emissions; however, the complex was non-emissive probably due to how the molecules arranged themselves in the stacking modules (Liang et al, 2020).…”

“…The complexes were made from hpzt and CuX (X = I, Br, and Cl) with a 1:3 ratio of the ligand to CuI yielding 32 consisting of two protonated ligands, connected by Cu + and I − in a distorted tetrahedral structure. The 2D structure was generated out of the interaction between Cu 6 S 6 and Cu 4 S 3 I units, creating short Cu…Cu bond distances, capable of influencing CC-assisted emissions; however, the complex was non-emissive probably due to how the molecules arranged themselves in the stacking modules ( Liang et al, 2020 ).…”

“…The next crystal 34 , with a monoclinic but P2/n space group, had its 3D outlook made via the connections between a copper metal with a tetrahedral shape formed from the coordination between two ligands and three chloride ions, with Cu 4 S 4 and a chloride ion serving as a bridge. On the other hand, 35 , an isostructural to [Cu 4 (pzt) 3 I]n, had an interaction between Cu 6 S 6 and Cu 2 Br 2 forming the 3D network ( Liang et al, 2020 ).…”

Synthesis, crystal structures and photoelectric properties of copper(I) alkynyl nanoclusters

“…如果给具有这类性能的团簇施加一定 电场, 在超过一定频率的光照下会有与结构相关的电流产生 [109~111] . 2020 年, Sun 课题组 [112] 用 Hpzt (吡嗪-2-硫醇)合成了一系列铜(I)团簇基聚合物, 具有良好的光致发光和光生 电流性质. 同时, 他们报道的 23 核四电子超原子炔铜(I)团簇 SD/Cu23a [74] 在 50 W、420 nm 光照和 0.6 V 的偏置电场作用下, 也具有良好的光生电流性质, 如图 10(f)所示.…”