Influence of Triplet State Multidimensionality on Excited State Lifetimes of Bis-tridentate Ru(II) Complexes: A Computational Study
Artikel i vetenskaplig tidskrift, 2012

Calculated triplet excited state potential energy surfaces are presented for a set of three bis-tridentate Ru(II)-polypyridyl dies covering a wide range of room temperature excited state lifetimes: [Ru(II)(tpy)(2)](2+), 250 ps; [Ru(II)(bmp)(2)](2+), 15 ns; and [Ru(II)(dqp)(2)](2+), 3 mu s (tpy is 2,2':6',2 ''-terpyridine, bmp is 6-(2-picoly1)-2,2'-bipyridine, and dqp is 2,6-di(quinolin-8-yl)Fridine). The computational results provide a multidimensional view of the (3)MLCT-(3)MC transition for the investigated complexes. Recently reported results of significantly prolonged (3)MLCT excited state lifetimes of bis-tridentate Ru(II)-complexes, for example [Ru(II)(dqp)(2)](2+), are found to correlate with substantial differences in their triplet excited state multidimensional potential energy surfaces. In addition to identification of low-energy transition paths for (3)MLCT-(3)MC conversion associated with simultaneous elongation of two or more Ru-N bonds for all investigated complexes, the calculations also suggest significant differences in (3)MLCT state volume in the multidimensional reaction coordinate space formed from various combinations of Ru-N bond distance varix:ions. This is proposed to be an important aspect for understanding the large differences in experimentally observed (3)MLCT excited state lifetimes. The results demonstrate the advantage of considering multidimensional potential energy surfaces beyond the Franck-Condon region in order to predict photophysical and photochemical properties of bis-tridentate Ru(II)-polypyridyl dyes and related metal complexes.

photophysical properties

artificial photosynthesis


ruthenium polypyridyl complexes



chelate complexes

density-functional theory





T. Osterman

Lunds universitet

Maria Abrahamsson

Chalmers, Kemi- och bioteknik, Fysikalisk kemi

Hans-Christian Becker

Chalmers, Kemi- och bioteknik, Fysikalisk kemi

L. Hammarström

Uppsala universitet

P. Persson

Lunds universitet

Journal of Physical Chemistry A

1089-5639 (ISSN) 1520-5215 (eISSN)

Vol. 116 1041-1050


Nanovetenskap och nanoteknik


Fysikalisk kemi