Influence of Triplet State Multidimensionality on Excited State Lifetimes of Bis-tridentate RuII Complexes: A Computational Study

Citations Over TimeTop 10% of 2011 papers

Abstract

Calculated triplet excited state potential energy surfaces are presented for a set of three bis-tridentate Ru(II)-polypyridyl dyes 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 μs (tpy is 2,2':6',2″-terpyridine, bmp is 6-(2-picolyl)-2,2'-bipyridine, and dqp is 2,6-di(quinolin-8-yl)pyridine). 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 variations. 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.

Related Papers

• → Spectroscopic constants and potential energy curves of PF(1995)23 cited
• → Multireference configuration interaction potential curve and analytical potential energy function of the ground and low-lying excited states of CdSe(2007)6 cited
• → A complete active space self-consistent field multiconfiguration reference configuration interaction study of the potential energy curves of the ground and excited states of CCl(2001)6 cited
• → Computational study on the O- and Cl-loss dissociations of ClOO(2018)1 cited
• → CASSCF and MRCI studies on the electronic excited states of CHBrO, CClBrO, and CBr2O(2000)2 cited