. Calculations show that the emissive triplet is of mixed MLCT/LLCT character. The emission is facilitated by the rigid tetrahedral structure, which is imposed by the tripod ligand. Accordingly, a distortion towards a square-planar geometry, which should occur upon MLCT excitation, is pre-

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The complexes Pt II (P−P)(CN) 2 with P−P = 1,2-bis(diphenylphosphanyl)benzene (dppb) and 2,2Ј-bis(diphenylphosphanyl)-1,1Ј-binaphthyl (binap) were synthesised and characterised by elemental analysis, ESI MS and electronic spectroscopy. The structure of Pt(dppb)(CN) 2 was resolved by single-crystal X-ray diffraction. This compound consists of mononuclear Pt II complexes with an almost planar PtP 2 C 2 coordination. While both complexes are not luminescent in solution, they show an emission in the solid state under ambient conditions. It is suggested that the luminescence of Pt(dppb)(CN) 2 originates from a (Pt II Ǟdppb) metal-to-ligand charge transfer (MLCT) triplet with some dppb intraligand (IL) contribution. This assignment is confirmed by calcula-

The aqueous complex shows two long-wavelength absorptions at A,,=647 and 372 nm which are assigned to Ru(II) to Ru(II1) and Ru(I1) to Co(II1) MMCT transitions, respectively. Photolysis of the aqueous solution led to a redox decomposition.Co" was formed with (p=2 X 10m4 at Ai,=577 and 0.18 at 366 nm. The electronic spectrum as well as the photoreactivity of the trinuclear complex are discussed on the basis of a Hush diagram which accommodates three redox-active metal centers.

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