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Two new calix[4]resorcinarene-based coordination cages adjusted by metal ions for the Knoevenagel condensation
Wen-Yuan Pei1, Bing-Bing Lu2, Jin Yang1
1Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun 130024, China. yangj808@nenu.edu.cn majf247@nenu.edu.cn.
Abstract:
Two new calix[4]resorcinarene-based coordination cages, namely, [Zn4(TPC4R)(PDC)4]·2DMF·6H2O (1-Zn) and [In11(TPC4R)2(PDC)16(μ2-OH)2(H2O)2]·[(CH3)2NH2]·8DMF·20H2O·EtOH (2-In), have been synthesized via solvothermal reactions (TPC4R = tetra(2-(4H-pyrazol-3-yl)pyridine)calix[4]resorcinarene, H2PDC = 3,5-pyridinedicarboxylic acid, DMF = N,N'-dimethylformamide). By carefully tuning different metal ions, two structurally different cages 1-Zn and 2-In were achieved. The former shows a bowl-shaped structure, while the latter features a dumbbell-like structure. After activation, they exhibited unsaturated Zn(ii) or In(iii) Lewis acid sites and the free nitrogen Lewis base sites of the PDC2-. Therefore, they were employed as catalysts for the Knoevenagel condensation reaction in the absence of a solvent. Particularly, 1-Zn featured high structural stability and enhanced the catalytic activity.
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