Influence of Triplet State Multidimensionality on Excited State Lifetimes of Bis-tridentate Ru(II) Complexes: A Computational Study
Journal article, 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.


ruthenium polypyridyl complexes




density-functional theory

chelate complexes

photophysical properties



artificial photosynthesis


T. Osterman

Lund University

Maria Abrahamsson

Chalmers, Chemical and Biological Engineering, Physical Chemistry

Hans-Christian Becker

Chalmers, Chemical and Biological Engineering, Physical Chemistry

L. Hammarström

Uppsala University

P. Persson

Lund University

Journal of Physical Chemistry A

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

Vol. 116 3 1041-1050

Areas of Advance

Nanoscience and Nanotechnology

Materials Science

Subject Categories

Physical Chemistry



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