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Two new calix[4]resorcinarene-based coordination cages adjusted by metal ions for the Knoevenagel condensation reaction
Dalton Transactions ( IF 3.5 ) Pub Date : 2021-07-06 , DOI: 10.1039/d1dt01139a
Wen-Yuan Pei 1 , Bing-Bing Lu 2 , Jin Yang 1 , Tianqi Wang 3 , Jian-Fang Ma 1
Affiliation  

Two new calix[4]resorcinarene-based coordination cages, namely, [Zn4(TPC4R)(PDC)4]·2DMF·6H2O (1-Zn) and [In11(TPC4R)2(PDC)162-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.

中文翻译:

用于Knoevenagel缩合反应的由金属离子调节的两种新型杯[4]间苯二酚基配位笼

两个新的杯[4]间苯二酚基配位笼,即[Zn 4 (TPC4R)(PDC) 4 ]·2DMF·6H 2 O ( 1-Zn ) 和[In 11 (TPC4R) 2 (PDC) 162 -OH) 2 (H 2 O) 2 ]·[(CH 3 ) 2 NH 2 ]·8DMF·20H 2 O·EtOH ( 2-In ),已通过溶剂热反应合成(TPC4R = tetra(2-( 4 H-吡唑-3-基)吡啶)杯[4]间苯二酚,H 2 PDC = 3,5-吡啶二甲酸,DMF = N, N'-二甲基甲酰胺)。通过仔细调整不同的金属离子,实现了两种结构不同的笼子1-Zn2-In。前者呈碗状结构,后者呈哑铃状结构。活化后,它们表现出不饱和的 Zn( II ) 或 In( III ) 路易斯酸位点和 PDC 2-的游离氮路易斯碱位点。因此,它们被用作在没有溶剂的情况下进行 Knoevenagel 缩合反应的催化剂。特别是1-Zn具有高结构稳定性和增强的催化活性。
更新日期:2021-07-06
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