用户名: 密码: 验证码:
Dynamic Jahn鈥揟eller Effect in the Metastable High-Spin State of Solvated [Fe(terpy)2]2+
详细信息    查看全文
文摘
Characterizing structural distortions in the metastable spin states of d4鈥揹7 transition metal ion complexes is crucial to understand the nature of their bistability and eventually control their switching dynamics. In particular, the impact of the Jahn鈥揟eller effect needs to be assessed for any electronic configuration that could be effectively degenerate, as in e.g. the high-spin (HS) manifold of highly symmetric homoleptic FeII complexes. However, capturing its manifestations remains challenging since crystallization generally alters the molecular conformations and their interconversion. With the rapid progress of ultrafast X-ray absorption spectroscopy, it is now possible to collect data with unprecedented signal-to-noise ratio, opening up for detailed structural characterization of transient species in the homogeneous solution phase. By combining the analysis of picosecond X-ray absorption spectra with DFT simulations, the structure of the photoinduced HS state is elucidated for solvated [Fe(terpy)2]2+ (terpy = 2,2鈥?6鈥?2鈥?terpyridine). This species can be viewed as the average 5B structure in D2 symmetry that originates from a dynamic Jahn鈥揟eller effect in the HS manifold. These results evidence the active role played by this particular instance of vibronic coupling in the formation of the HS state for this benchmark molecule. Ultimately, correlating the interplay between intramolecular and intermolecular degrees of freedom to conformational strain and distortions in real time should contribute to the development of advanced functionalities in transition metal ion complexes.

© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号

地址:北京市海淀区学院路29号 邮编:100083

电话:办公室:(+86 10)66554848;文献借阅、咨询服务、科技查新:66554700