Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal‐Centered Excited State in the Bond Rupture and Bond Construction Processes |
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| Authors: | Dr Huifang Li Lisheng Zhang lvyin Zheng Dr Xun Li Dr Xiaolin Fan Dr Yi Zhao |
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| Institution: | 1. Key Laboratory of Organo-Pharmaceutical Chemistry, Gannan Normal University, Ganzhou, P. R. China;2. State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, P. R. China |
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| Abstract: | Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, Ru(L)(tpy)(DMSO)]n+ (where tpy=2,2’:6’,2’’‐terpyridine; DMSO=dimethyl sulfoxide; L=2,2’‐bipyridine (bpy), n=2; N,N,N’,N’‐tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal‐centered ligand field (3MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of 3MCS state is thermally accessible and no 3MCO can be populated from this state, photoisomerization will be turned off because the 3MCS excited state is expected to lead to fast radiationless decay back to the original 1GSS ground state or photodecomposition along the Ru2+?S stretching coordinate. On the contrary, if the population of 3MCS (or 3MCO) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal‐to‐ligand charge transfer excited states (3MLCTS→3MLCTO). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d6 transition‐metal complexes, which is both experimentally and intellectually challenging as a field of study. |
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| Keywords: | density functional calculations photochromic mechanisms organometallic chemistry photochemistry ruthenium |
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