四川大学学报（自然科学版）2026，Vol.63Issue(1)：127-138,12.DOI:10.19907/j.0490-6756.250079
手性邻碳硼烷衍生物的光学性质研究
Optical properties of chiral o-carborane derivatives
摘要
Abstract
o-carborane is an excellent luminescent material that has attracted significant attention in recent years.It has remarkable advantages,including high chemical stability,high thermal stability,and high lumi-nous intensity.As a result,it has been extensively studied by researchers.Amino acids,being common chi-ral molecules in nature with a rich variety of side-chain groups,are capable of interacting with other molecules to influences the optical properties of the system.The transmission,amplification,and regulation of chiral signals can be achieved.Combining density functional theory calculations and molecular dynamics calcula-tions,cysteine(Cys)was introduced into luminescent o-carborane derivatives.The resulted chiral molecule,named Cysteine(S*)-bi(benzo[b]thiophene)-fused o-carborane(CFOC),has a high g-factor for circular dichro-ism and large absorption oscillator strength,and exhibits a strong circular dichroism signal in the ultraviolet range.The influence of the binding mode of chiral ligand on the electronic structure of o-carborane derivatives was analyzed.The proportions of different configurations within the temperature range from 50 K to 500 K were estimated by Boltzmann distribution.The dominant configurations are 12-C(S*)FOC,6-C(COO*)FOC,and 6-C(NH*)FOC in sequence.CFOC exhibits new spectral characteristics which originate from the reduc-tion in symmetry caused by the modification of Cys.The circular dichroism(CD)signal originates from the deflection of the transition magnetic dipole moment and the transition electric dipole moment.The relation-ships among the CD signal,the absorption oscillator strength,and the excitonic characteristics were ex-plored.The variation of the chiral optical spectra with temperature was also discussed.Our results show that the charge transfer(CT)excitation between ligand and the fluorophore is the source of strong CD signal.The g factor of CFOC is on the order of 10-3.The exciton lifetime of CFOC is approximately 35 ns,and a few isomer configurations reach 0.5 μs.At low temperatures,CFOC exhibits higher chiral activity,and the spec-tral shape changes noticeably.Molecular dynamics calculations show that 12-C(S*)FOC has good thermal sta-bility at both 300 K and 500 K.These insights provide valuable guidance for the experimental synthesis of new chiral luminescent o-cariborane derivatives.关键词
手性配体/邻碳硼烷/圆二色性/g因子Key words
chiral ligand/o-carborane/circular dichroism/g-factor分类
数理科学引用本文复制引用
姜泓,杨小伟,韩萍萍,周思..手性邻碳硼烷衍生物的光学性质研究[J].四川大学学报（自然科学版）,2026,63(1):127-138,12.基金项目
国家自然科学基金(12222403,12474168) （12222403,12474168）
