New High-Pressure Gallium Borate Ga2B3O7(OH) with Photocatalytic Activity.

The new high-pressure gallium borate Ga2B3O7(OH) was synthesized in a Walker-type multianvil apparatus under high-pressure/high-temperature conditions of 10.5 GPa and 700 °C. For the system Ga-B-O-H, it is only the second known compound next to Ga9B18O33(OH)15·H3B3O6·H3BO3. The crystal structure of Ga2B3O7(OH) was determined by single-crystal X-ray diffraction data collected at room temperature. Ga2B3O7(OH) crystallizes in the orthorhombic space group Cmce (Z = 8) with the lattice parameters a = 1050.7(2) pm, b = 743.6(2) pm, c = 1077.3(2) pm, and V = 0.8417(3) nm(3). Vibrational spectroscopic methods (Raman and IR) were performed to confirm the presence of the hydroxyl group. Furthermore, the band gap of Ga2B3O7(OH) was estimated via quantum-mechanical density functional theory calculations. These results led to the assumption that our gallium borate could be a suitable substance to split water photocatalytically, which was tested experimentally.

Luminescent dinuclear Cu(I) complexes containing rigid tetraphosphine ligands.

The synthesis and the photophysics of three dinuclear copper(I) complexes containing bis(bidentate)phosphine ligands are described. The steric constraint imposed by tetrakis(di(2-methoxyphenyl)phosphanyl)cyclobutane) (o-MeO-dppcb) in combination with 2,9-dimethyl-1,10-phenanthroline in one of the complexes leads to interesting photophysical properties. The compound shows an intense emission at room temperature in deoxygenated acetonitrile solution (Φ = 49%) and a long excited-state lifetime (13.8 µs). Interestingly, at low temperature, 77 K, the emission maximum shifts to lower energy, and the excited-state lifetime increases. This observation leads to the conclusion that a mixing between the excited triplet and singlet states is possible and that the degree of mixing and population of state strongly depends on temperature, as the energy difference is quite small. The electroluminescent properties of this compound were therefore tested in light-emitting electrochemical cells (LEECs), proving that the bright emission can also be obtained by electrically driven population of the singlet state.

Oxidative quenching within photosensitizer-acceptor dyads based on bis(bidentate) phosphine-connected osmium(II) bipyridyl light absorbers and reactive metal sites.

For the first time oxidative quenching of OsP2N4 chromophores by reactive PtII or PdII sites containing cis, trans, cis-1,2,3,4-tetrakis(diphenylphosphino)cyclobutane (dppcb) is directly observed despite the presence of a saturated cyclobutane backbone "bridge". This dramatic effect is measured as a sudden temperature-dependent onset of a reduction in phosphorescence lifetime in [Os(bpy)2(dppcb)MCl2](SbF6)2 (M = Pt, 1; Pd, 2). The appearance of this additional energy release is not detectable in [Os(bpy)2(dppcbO2)](PF6)2 (3), where dppcbO2 is cis, trans, cis-1,2-bis(diphenylphosphinoyl)-3,4-bis(diphenylphosphino)cyclobutane. Obviously, the square-planar metal centers in 1 and 2 are responsible for this effect. In line with these observations, the emission quantum yields at room temperature for 1 and 2 are drastically reduced compared with 3. Since this luminescence quenching implies strong intramolecular interaction between the OsII excited states and the acceptor sites and depends on the metal⋯metal distances, also the single crystal X-ray structures of 1-3 are given.