Wang Chih-Chieh, Liao Pei-Juan, Chung Yu-Chen, Shin Chi-Yang, Wu Yi-Chen, Lee Gene-Hsiang, Chien Su-Ying, Chen Bo-Hao, Chuang Yu-Chun
Department of Chemistry, Soochow University, 11102 Taipei, Taiwan.
Instrumentation Center, National Taiwan University, 10617 Taipei, Taiwan.
ACS Omega. 2024 Sep 18;9(39):40920-40931. doi: 10.1021/acsomega.4c06176. eCollection 2024 Oct 1.
Three supramolecular architectures, [Cu(dpds)(CO)(HO)]·3HO (), [Cu(dpds)(CO)]·3HO (), and [Cu(dpds)(CO)]·9HO·CHOH () (dpds = 4,4'-dipyridyldisulfide and CO (croconate) = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione), have been synthesized and structurally characterized. Compound contains two crystallographically independent Cu(II) ions, which are both distorted octahedral geometry with elongation along the croconate- and HO-bound axial positions and bonded with two N atoms of two dpds, two O atoms of one CO , and two HO molecules. Two crystallographically independent dpds ligands, both adopting the bis-monodentate bridging mode, connect two Cu(II) ions to form a one-dimensional zigzag chain-like coordination polymer. In and , there are two and three crystallographically independent Cu(II) ions, respectively, which are all distorted octahedral geometries with elongation along the croconate-bound axial positions six-coordinated and bonded with two N atoms of two dpds ligands in cis- or/and trans-forms and four O atoms of two CO ligands. The dpds ligands in and all adopt the bis-monodentate bridging mode, and the CO ligands act as bridging ligands with bridging bis-bidentate through three CO oxygen atoms in and bridging bis-bidentate through four adjacent CO oxygen atoms in , respectively, linking the Cu(II) ions to generate a two-dimensional layered and a three-dimensional metal-organic framework, respectively. The structural diversity and dimensionality observed in - may be attributed to the cis- or/and trans-coordination sphere of Cu(II) centers with two dpds ligands and the coordination modes of croconate ligands. Thermal stability and in situ temperature-dependent structural variations of - have been verified by thermogravimetric analysis and powder X-ray diffraction measurements. Compounds and both exhibit water vapor capture behaviors with hysteresis isotherms.
已合成并对三种超分子结构[Cu(dpds)(CO)(HO)]·3HO ()、[Cu(dpds)(CO)]·3HO ()和[Cu(dpds)(CO)]·9HO·CHOH ()（dpds = 4,4'-二吡啶二硫化物，CO （环戊烯酮）= 4,5 -二羟基环戊 - 4 -烯 - 1,2,3 -三酮的二价阴离子）进行了结构表征。化合物 包含两个晶体学独立的Cu(II)离子，二者均为畸变八面体几何构型，沿环戊烯酮和HO配位的轴向位置拉长，并与两个dpds的两个N原子、一个CO 的两个O原子以及两个HO分子键合。两个晶体学独立的dpds配体均采用双单齿桥连模式，连接两个Cu(II)离子形成一维锯齿链状配位聚合物。在 和 中，分别有两个和三个晶体学独立的Cu(II)离子，它们均为畸变八面体几何构型，沿环戊烯酮配位的轴向位置拉长，六配位，并与两个dpds配体的两个N原子以顺式或/和反式形式以及两个CO 配体的四个O原子键合。 和 中的dpds配体均采用双单齿桥连模式，CO 配体分别作为桥连配体，在 中通过三个CO 氧原子以双齿桥连，在 中通过四个相邻的CO 氧原子以双齿桥连，连接Cu(II)离子分别生成二维层状和三维金属有机骨架。在 - 中观察到的结构多样性和维度可能归因于Cu(II)中心与两个dpds配体的顺式或/和反式配位环境以及环戊烯酮配体的配位模式。通过热重分析和粉末X射线衍射测量验证了 - 的热稳定性和原位温度依赖性结构变化。化合物 和 均表现出具有滞后等温线的水蒸气捕获行为。
