Spectroscopic and Electrochemical Properties of Electronically Modified Cycloplatinated Formazanate Complexes.

Formazanates are a class of monoanionic, chromophoric, redox-active chelating ligands, and until recently, the coordination chemistry of formazanates with third-row transition metals was unexplored. Described here is a series of heteroleptic cyclometalated platinum formazanate complexes of the type Pt(C^N)(Fz), where "C^N" is the cyclometalating ligand and "Fz" is the formazanate. This work includes a set of 14 complexes derived from four different cyclometalating ligands and five different formazans, greatly expanding the structural and electronic diversity of this class of complexes. The formazans fall into two major categories: triarylformazans with either electron-donating (Me, OMe) or electron-withdrawing (CN) para substituents, and even more electron-deficient diarylformazans where the center position of the backbone is a cyano group. Seven of the new compounds are characterized by single-crystal X-ray diffraction, and all are characterized by cyclic voltammetry and UV-vis absorption spectroscopy to provide insight into the frontier orbitals. The complexes can be electrochemically reduced by three electrons, with the first two electrons populating formazanate-centered frontier orbitals and the third being added to the Pt-C^N fragment. The formazanate-based reduction potentials are highly sensitive to the substitution pattern of the formazanate and can be tuned over a wide range of ca. 0.8 V by altering substituents. The formazanates also impart these complexes with very strong, low-energy visible absorption bands assigned to HOMO → LUMO transitions, which are greatly perturbed from the free ligand due to interactions of the formazanate frontier orbitals with platinum-centered orbitals. Unlike the redox properties, the formazanate-derived visible absorption band is relatively insensitive to substituent effects. Additional visible absorption bands, attributed to Pt(d) → C^N(π*) MLCT transitions, can be tuned over a wide range by changing the structure of the C^N ligand, giving rise to strong panchromatic absorption for some members of the series.