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A general method for synthesizing a novel class of metalloporphyrin dimers containing unbridged metal-metal bonds is presented. By choosing the appropriate metal, the bond order in these dimers can be varied systematically. The synthesis and characterization of osmium(II) and molybdenum(II) porphyrin dimers containing the respective metal-metal double and quadruple bonds are described. A simple molecular orbital treatment that accounts for the metal-metal bonding, spin state, and geometry in these complexes is discussed.

Systematic variation of metal—metal bond order in metalloporphyrin dimers