2010302010093 ; 化學系 ; We have prepared and characterized a series of osmium complexes [Os-2(CO)(4)(fpbPY)(2)] (1), [OS(CO)(fpbpY)(2)] (2), and [Os(fpbpy)(2)] (3) with tridentate 6-pyrazol-3-yl 2,2'-bipyridine chelating ligands. Upon the transformation of complex 2 into 3 through the elimination of the CO ligand, an extremely large change in the phosphorescence wavelength from 655 to 935 nm was observed. The results are rationalized qualitatively by the strong pi-accepting character of CO, which lowers the energ of the osmium d(pi) orbital, in combination with the lower degree of T conjugation in 2 owing to the absence of one possible pyridine-binding site. As a result, the energy gap for both intraligand pi-pi* charge transfer (ILCT) and metal-to-ligand charge transfer (MLCT) is significantly greater in 2. Firm support for this explanation was also provided by the time-dependent DFT approach, the results of which led to the conclusion that the S-o -> T-1 transition mainly involves MLCT between the osmium center and bipyridine in combination with pyrazolate-to-bipyridine 3 pi-pi* ILCT. The relatively weak near-infrared emission can be rationalized tentatively by the energy-gap law, according to which the radiationless deactivation may be governed by certain low-frequency motions with a high density of states. The information provided should allow the successful design of other emissive tridentate metal complexes, the physical properties of which could be significantly different from those of complexes with only a bidentate chromophore.