化学
环加成
环丁烷
氢键
配位聚合物
光化学
单晶
产量(工程)
结晶学
三键
氢
分子
晶体结构
研磨
Crystal(编程语言)
双键
高分子化学
催化作用
有机化学
材料科学
戒指(化学)
计算机科学
程序设计语言
冶金
复合材料
作者
Hasan Ali Al-Mohsin,Ammar AlMousa,Sulayman A. Oladepo,Almaz S. Jalilov,Mohammed Fettouhi,Abdul Malik Puthan Peedikakkal
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2019-07-18
卷期号:58 (15): 10167-10173
被引量:19
标识
DOI:10.1021/acs.inorgchem.9b01276
摘要
A one-dimensional hydrogen-bonded triple-stranded ladder coordination polymer [Cd(bpe)1.5(NO3)2(H2O)] (1) (where bpe = trans-1,2-bis(4-pyridyl)ethylene) containing three parallel C═C double bonds was synthesized. This compound undergoes photochemical [2 + 2] cycloaddition and produces rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) in up to 67% yield via Single-Crystal-to-Single-Crystal (SCSC) transformation. Triple-stranded ladder-like structures have never before displayed such a kind of SCSC transformation. Furthermore, photoirradiation of ground 1 produces rctt-tpcb in up to 100% yield in the solid state. On the basis of the alignment of three C═C olefinic bonds of bpe ligands in parallel, only two out of the three aligned bpe are expected to undergo [2 + 2] photodimerization. However, the quantitative yield from the solid-state photochemical [2 + 2] cycloaddition reaction has been achieved via grinding of crystals of 1 to a powder. The effects of grinding on photoreactivity of 1 were thoroughly studied using 1H NMR spectroscopy, thermogravimetric analysis (TGA), and Raman spectroscopy. These studies indicate that the molecular movements of the hydrogen-bonded ladders are reinforced due to the loss of coordinated water molecules and the further crystal repacking via bond-breaking/forming of the hydrogen-bonded assemblies during mechanical grinding. The 100% photodimerization of ground 1 shows that the grinding accelerates internal molecular motions of ladder structures within the crystals lattice. The solid-state photoluminescence of 1, before and after UV irradiation, was investigated at room temperature, both indicative of interesting luminescent properties.
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