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Capturing the Organic Species Derived from the C–C Cleavage and in Situ Oxidation of 1,2,3,4-Tetra(pyridin-4-yl)cyclobutane by [CuCN]n‑Based MOFs

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journal contribution
posted on 25.07.2018, 19:03 by Liang Chen, Hong-Xi Li, Ming Dai, Hai-Yan Li, Jian-Ping Lang
The solvothermal cycloreversion and in situ oxidation of 1,2,3,4-tetra­(pyridin-4-yl)­cyclobutane (tpcb) within [CuCN]n-based MOFs were investigated. The radical mechanism for the cycloreversion of tpcb ligands was supported by capturing a 1,3-butadiene species 1,2,3,4-tetra­(4-pyridyl)-1,3-butadiene (tpyb) into {[Cu18­(μ-CN)18­(tpcb)4­(tpyb)2]·H2O}n in the presence of 2,2,6,6-tetra­methyl­piperidine-1-oxyl (TEMPO). Without TEMPO, a furan-based ligand 2,3,4,5-tetra­(4-pyridyl)­furan (tpyf) was generated within {[Cu4­(μ-CN)4­(tpyf)]·4MeCN}n via the C–C cleavage, followed by in situ oxidation in acidic condition.