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

Liwei Zhao, Hua-Jun Fan


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.


Full Text:



  • There are currently no refbacks.