Ab Initio Investigating the Bonding and Electronic Structure in Bismuth Calixarene Complexes

Liwei Zhao, Hua-Jun Fan

Abstract


The geometric and electronic structures of calixarene bismuth(III) complexes have been investigated by ab initio method in this study. Three conformations (cone shape conformation with C2v symmetry, 1,2-alternative conformation with C2h symmetry and 1,3-alternative conformation) are investigated as possible binding modes between bismuth fragment and calixarene fragment. The optimized geometries are then compared with the recent reported crystal structure. Two bis-muth(III) fragments are needed to bind with calixarene ligand due to the inert-pair effect. Co-crystalized LiCl-DMSO fragment plays a crucial role in stabilizing the bismuth calixarene crystal, where the binding energy ΔH is estimated to be 55.3 kcal/mol or 56.1 kcal/mol with zero-point energy correction. The estimated ΔG is -28.2 kcal/mol for the complex, which is consistent with the strong HC4Bi-ClLi interactions. The trans effect is evidenced by two slight longer Bi-O bond lengths.


DOI
10.12783/dtetr/apetc2017/10894

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