Supramolecular Chemistry ( IF 3.3 ) Pub Date : 2021-08-09 , DOI: 10.1080/10610278.2021.1959920 Chao Shen 1 , Rene Z. H. Phe 1 , Isabella Fong 1 , Alexandre N. Sobolev 2 , Mauro Mocerino 1 , Massimiliano Massi 1 , Mark I. Ogden 1
ABSTRACT
Driven by an interest in the impact of the para-substituent of calix[4]arenes on metal complexation and structural chemistry, studies of p-cyclohexylcalix[4]arene (L) have been carried out. The 1:1 dichloromethane and dimethylformamide solvates were found to be isostructural, and different to the typical bilayer structure often observed for p-t-butylcalix[4]arene solvates. The methanol solvate, in contrast, does form a bilayered structure but is also a 1:1 solvate, unlike the p-t-butylcalix[4]arene·2MeOH system. Lanthanoid complexation was investigated, resulting in the structural characterisation of two different DMF solvates of a 2:2 dimeric europium complex, Eu2(L–3H)2(DMF)4. A tetrazole derivative, 5,11,17,23-tetracyclohexyl-25,27-dihydroxy-26,28-bis(tetrazole-5-ylmethoxy)calix[4]arene, has been synthesised via the intermediate 5,11,17,23-tetracyclohexyl-25,27-dihydroxy-26,28-dicyanomethoxycalix[4]arene, with the latter compound being structurally characterised. Attempts to isolate lanthanoid clusters supported by the tetrazole derivative under conditions known to form Ln19 clusters with the p-t-butyl analogue were unsuccessful, resulting only in isolation of the ligand from the reaction mixture.
中文翻译:
对环己基杯[4]芳烃的结构、衍生化和金属络合
摘要
由于对杯[4]芳烃的对位取代基对金属络合和结构化学的影响的兴趣,已经开展了对环己基杯[4]芳烃(L)的研究。发现 1:1 二氯甲烷和二甲基甲酰胺溶剂化物是同构的,与对叔丁基杯[4]芳烃溶剂化物经常观察到的典型双层结构不同。相比之下,甲醇溶剂化物确实形成双层结构,但也是 1:1 溶剂化物,这与对叔丁基杯[4]芳烃·2MeOH 体系不同。对镧系元素络合进行了研究,从而对 2:2 二聚铕络合物 Eu 2 (L–3H) 2 (DMF)的两种不同 DMF 溶剂化物进行了结构表征4 . 通过中间体 5,11,17 合成了四唑衍生物 5,11,17,23-tetracyclohexyl-25,27-dihydroxy-26,28-bis(tetrazole-5-ylmethoxy)calix[4]arene, 23-四环己基-25,27-二羟基-26,28-二氰基甲氧基杯[4]芳烃,后一种化合物具有结构特征。在已知与对叔丁基类似物形成Ln19簇的条件下分离由四唑衍生物支持的镧系元素簇的尝试未成功,仅导致从反应混合物中分离出配体。