Structural and electronic properties of chemically modified fullerenes

Abstract

ABSTRACTChemically modified fullerenes are emerging as an important class of technological materials. This study deals with one such category of modified fullerenes, viz., heterofullerenes. Structure-property relationships of Pd, Ni and N-substituted heterofullerenes were probed using density functional theory calculations. Distortion in spheroid of C cage during formation of three different heterofullerenes, viz., CM, CNM and CNM (), was analyzed from DFT optimised geometries and13C NMR characterisation. NBO analysis was done to identify the strength of bonds based on their bond orders and coordination of metal M with C and N atoms. Extent of delocalisation of π electrons in terms of aromaticity of C after foreign atoms substitution was examined by NICS(0) characterisation. HOMO-LUMO gap, ionisation potential, electron affinity and chemical potential were calculated to obtain insights into the reactivities and stabilities of the heterofullerenes with reference to C. Amongst CM, CNM and CNM heterofullerenes, CNM and CNM were concluded to be the most stable and reactive heterofullerenes, respectively.