Metal diimine-dithiolene complexes

The most detailed spectroscopic and electronic structure studies of metallo-mono(dithiolenes) have focused on the nature of ligand-to-ligand charge transfer (LLCT) excitations in [M(diimine)(dithiolene)] complexes (112, 250-257, 262, 264, 295-301) and in monooxo molybdenum dithiolenes (19, 20, 22, 23) as models for pyranopterin molybdenum enzymes such as sulfite oxidase (SO). Since metallo-mono(dithiolenes) generally possess little or no symmetry, detailed spectrosopic and electronic structure studies of this class of metallo-dithiolenes have only recently begun to appear. The analysis of the spectroscopic data has been aided by the fact that the dithiolene-to-metal charge... 

Square-planar metallo(diimine)(dithiolene) complexes generally display intense, solvatochromatic absorptions in the visible region of the spectrum that are not found in the corresponding metallo-bis(dithiolene) or metallo-bis (diimine) complexes. Futhermore, the LLCT transition energy does not vary appreciably as a function of the metal ion. Extended Hiickel calculations on Ni, Pt, and Zn metallo(diimine)(dithiolene) complexes indicate that the HOMO is comprised almost entirely of dithiolene orbital character (Figure 2), while the LUMO was found to possess essentially all diimine n orbital character (112, 252, 268). In stark contrast to the spectra of square-planar Ni and Pt metallo (diimine)(dithiolene) complexes, the psuedo-tetrahedral complexes of Zn possess extremely weak LLCT transitions. Now, it is of interest to discuss the differences in LLCT intensity as a function of geometry from a MO point of view. This discussion should help to explain important orientation-dependent differences in photoinduced electron delocalization and charge separation. 

The combination of dithiolene and diimine chelating ligands in square-planar ds complexes gives rise to a unique CT excited state, and complexes of this class have been the subject of a rich and growing amount of research in recent years. The Pt(diimine)(dithiolene) complexes were among the earliest examples of emission from square-planar metal complexes in fluid solution. Luminescence from room temperature solutions of Pt(diimine)(mnt) complexes with diimine = bpy, phen, or an alkyl- or aryl-substituted derivative was reported in 1990 by Zuleta et al. (98, 99), following an initial report on similar complexes with a 1,1-dithiolate. 

With rich luminescent properties, long-lived CT excited states and a variety of bimolecular photochemical reaction pathways, the mixed-ligand square-planar diimine dithiolene complexes of d8 metal ions show great promise for solar-energy conversion, as luminescent probes or in photocatalytic applications. Complexes of this type have also received attention for the nonlinear optical properties, such as second harmonic generation, related to the MMLL CT excited state (14, 129). 

These complexes are redox active. The two one-electron reductions resemble more closely the reduction of the corresponding bis(diimine) complex than those of the corresponding bis(dithiolene) complex. The redox potentials are more sensitive to diimine ligand variation than to dithiolene variation. One-electron oxidation is relatively insensitive to diimine ligand variation. However, the dependence of one-electron oxidation on dithiolene variation has not been assessed directly due to the limited amount of data available on the oxidation of the corresponding dithiolene complexes. It has been proposed that the LUMO of the neutral mixed-dithiolene diimine complexes possesses more diimine than dithiolene character and that the HOMO is mainly metal d orbital in nature (52). 

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