The synthesis, characterization, electrochemistry, photophysics and photochromic behavior of a new class of cyclometalated platinum(II) complexes [Pt(C(∧)N)(O(∧)O)] (1a-5a and 1b-5b), where C(∧)N is a cyclometalating 2-(2'-thienyl)pyridyl (thpy) or 2-(2'-thienothienyl)pyridyl (tthpy) ligand containing the photochromic dithienylethene (DTE) unit and O(∧)O is a β-diketonato ligand of acetylacetonato (acac) or hexafluoroacetylacetonato (hfac), have been reported. The X-ray crystal structures of five of the complexes have also been determined. The electrochemical studies reveal that the first quasi-reversible reduction couple, and hence the nature of lowest unoccupied molecular orbital (LUMO) of the complexes, is sensitive to the nature of the ancillary O(∧)O ligands. Upon photoexcitation, complexes 1a-3a and 1b-3b exhibit drastic color changes, ascribed to the reversible photochromic behavior, which is found to be sensitive to the substituents on the pyridyl ring and the extent of π-conjugation of the C(∧)N ligand as well as the nature of the ancillary ligand. The thermal bleaching kinetics of complex 1a has been studied in toluene at various temperatures, and the activation barrier for the thermal cycloreversion of the complex has been determined. Density functional theory (DFT) calculations have been performed to provide an insight into the electrochemical, photophysical and photochromic properties.

A versatile dithienylethene-containing β-diketonate ligand and its boron(III) compounds have been successfully synthesized. Upon photocyclization, the ligand shows a new absorption band at 630 nm with good fatigue resistance and high thermal stability. Incorporation of the boron center has been demonstrated to shift the photochromic behavior to the NIR region.

The straightforward synthesis of a new Cu(i) metal-rich small metallacycle is presented. This compound is luminescent in the solid state with an emission quantum yield of 72% at room temperature and displays a pronounced reversible red-shift of its emission spectra upon cooling. Quantum chemical calculations reveal that these properties are governed by important geometrical relaxations that imply the formation of cuprophilic interactions at the excited states.