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[10] The stimulated emission spectrum was calculated from the spontaneous emission spectrum of the sample excited at λexc=515 nm (Qx(1,0) band) and at λexc=550 nm (Qx(0,0) band), which were recorded on a HITACHI model F-4500 fluorescence spectrophotometer, using the relation between the Einstein coefficients Anm (spontaneous emission) and Bnm(stimulated emission) given by Anm=(2hc/λ3)Bnm.

[11] (a) LIM M H, LIPPARD S J. Inorg. Chem. 2004, 43, 6366-6370. That (λmax=556 nm) of RuⅡ(OEP)(CO)(py) (b) Hopf. F. R., O’Brien. T. P., Scheidt. W. R., Whitten. D. G. Structure and reactivity of ruthenium(II) porphyrin complexes. Photochemical ligand ejection and formation of ruthenium porphyrin dimmers［J］. J. Am. Chem. Soc., 1975,97(2):277-281.

     The fluorescence spectra (λmax=560 nm) of RuⅡ(TPP)(CO)(dansyl-imidazole)

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[13] Geometry optimizations were performed with B3LYP/6-31G* for model RuII(CO)(por).

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[14] The metal-complex structure change during the chemical reaction causes the intersystem crossing.

     See also, Ref. 4(a) and (b).

     (b) IWAKURA I, IKENO T, YAMADA T. A DFT study on Hetero-Diels-Alder reactions catalyzed by cobalt complexes:lewis acidity enhancement as a consequence of spin transition caused by lewis base coordination［J］. Angew. Chem. Int. Ed., 2005,44(17):2524-2527.

     (a) KHAVRUTSKII I V, MUSAEV D G, MOROKUMA K. Structure, Stability, and Electronic and NMR Properties of Various Oxo- and Nitrido-Derivatives of ［L(Salen)Mn(III)］+, Where L = None and Imidazole. A Density Functional Study［J］. Inorg. Chem., 2003,42(8):2606-2621.

[15] (d) BRESSLER C, MILNE C, PHAM V T,et al.. Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex［J］. Science, 2009,323:489-492.

     (e) KOBAYASHI T,STRAUB K D, RENTZEPIS P M. Energy relaxation mechanism in Ni(II), Pd(II), Pt(II) and Zn(II) porphyrins［J］. Photochem. Phhotobiol., 1979,29(5):925-931.

     (b) GAWELDA W, CANNIZZO A, PHAM V T,et al.. Ultrafast nonadiabatic dynamics of ［FeⅡ(bpy)3］2+ in solution［J］. J. Am. Chem. Soc., 2007,129(26):8199-8206.

     (c) CANNIZZO A, BLANCO-RODRIGUEZ A M, NAHHAS A E,et al.. Femtosecond Fluorescence and Intersystem Crossing in Rhenium(I) Carbonyl Bipyridine Complexes［J］. J. Am. Chem. Soc., 2008,130(28):8967-8974.

     The heavy-atom effect is reported not to be a critical parameter in intersystem crossing of 1MLCT→3MLCT of M(bpy)3 complex in ref. (a-d). On the other hand, the heavy-atom effect was observed in intersystem crossing of 1(π,π*)→3(π,π*) of M protoporphyrin in ref. (e). The existence of the heavy atomic effect is not sure in the present work of 1(π,π*)→3(d,π*). Therefore, just a possibility of the heavy atomic effect was mentioned in the manuscript.

     (a) CANNIZZO A, MOURIK F, GAWELDA W, et al.. Broadband Femtosecond Fluorescence Spectroscopy of ［Ru(bpy)3］2+ ［J］. Angew. Chem. Int. Ed., 2006,45(19):3174-3176.