Excited-state distortions determined from structured luminescence of nitridorhenium(V) complexes

被引：18

作者：

Bailey, SE ^{[1
]}

Eikey, RA ^{[1
]}

Abu-Omar, MM ^{[1
]}

Zink, JI ^{[1
]}

机构：

[1] Univ Calif Los Angeles, Dept Biochem & Chem, Los Angeles, CA 90095 USA

来源：

INORGANIC CHEMISTRY | 2002年 / 41卷 / 07期

关键词：

D O I：

10.1021/ic010680m

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The nitridorhenium(V) complexes ReNCl2(PCy3)(2) (1), ReNBr2(PCy3)(2) (2), ReNCl2(PPh3)(2) (3), and ReNBr2(PPh3)(2) (4) produce structured emission spectra upon excitation at low temperature. The origin, E-00, occurs at 15 775, 16 375, 15 875, and 16 300 cm(-1), respectively. The vibronic peaks are regularly spaced with an average energy separation corresponding to the RedropN stretching frequency. The nitridorhenium stretching frequency ranges from 1095 to 1101 cm(-1), as determined by Raman and IR spectroscopy. The excited-state distortions are calculated by fitting the emission spectra. The excited state arises primarily from a d(xy) (ReN nonbonding) to d(yz) (ReN pi antibonding) transition. The rhenium-nitrogen bond length in the excited state is 0.08 Angstrom longer than in the ground electronic state, which is consistent with the difference in bond lengths of ReN bonds of bond order 3 and bond order 2.5 as determined from molecular structures.

引用

页码：1755 / 1760

页数：6

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