Theoretical Insights into the Formation and Optical Properties of C 60 out and C 60
Xiao Huang, Yong‐Bi Wang, Feng‐Wei Gao, Rong‐Lin Zhong, Zhong‐Min SuABSTRACT
This work investigates how the spatial arrangement of host‐guest complexes influences their nonlinear optical (NLO) responses, focusing on the isomerism of cycloparaphenylene (CPP) and fullerene (C 60 ) systems. Using density functional theory (DFT), we compare the geometry and NLO properties of C 60 located inside (C 60 in ) and outside (C 60 out ) of boron‐ and nitrogen‐doped nanorings (BCP and NCP). C 60 in form is more stable due to strong dispersion interactions, while C 60 out isomers yield significantly higher first hyperpolarizabilities ( β tot ). This performance difference arises from the distinct charge‐transfer (CT) pathways, where C 60 out @BCP exhibits large intramolecular CT within the host, whereas C 60 out @NCP induces a new intermolecular CT process from the host to the guest. Furthermore, C 60 out form exhibits high sensitivity to external electric fields, allowing for effective modulation of second‐order NLO responses. These findings propose that C 60 out form is distinct from the traditional C 60 @[10]CPP, offering new idea for designing high‐efficiency organic optoelectronic materials.