Photophysical and electrochemical properties of Ru(II) complexes containing tridentate bisphosphino-oligothiophene ligands.

Nine Ru(II) complexes containing the conjugated oligothiophene ligands 3,3''-bis(diphenylphosphino)-2,2':5',2''-terthiophene (P(2)T(3)) and 4',3'''-bis(diphenylphosphino)-3,3''''-dihexyl- 2,2':5',2'':5'',2''':5''',2''''-pentathiophene (P(2)T(5)) were prepared and characterized. P(2)T(3) and P(2)T(5) bond as tridentate ligands and three of the complexes (1, 2 and 5) form green five-coordinate Ru(II) complexes in solution. Cyclic voltammetry, variable temperature UV-vis spectroscopy and time-resolved transient absorption spectroscopy were used to characterize the electronic properties of the complexes.

Photophysical properties and electropolymerization of gold complexes of 3,3''-diethynyl-2,2':5',2''-terthiophene.

The preparation and crystal structures of 3,3''-diethynyl-2,2':5',2''-terthiophene (A(2)T(3)) and three Au(I) complexes containing this ligand are reported. One of the complexes, Au(2)(dppm)(A(2)T(3)), has a short Au-Au distance (3.1969 A) because of an aurophilic interaction.

Conjugated ligand-based tribochromic luminescence.

A Au(I) complex containing a terthienyl diphosphine ligand is non-emissive in the crystalline form, but exhibits intense ligand-based emission upon grinding attributed to increased planarization in the terthienyl ligand.

Synthesis, structures, and kinetics of mixed-donor amido-amino-siloxo ligands from symmetrical diamidosilyl ether ligands via a retro-brook rearrangement.

Deprotonation of the new (R = propyl, 3,5-Me(2)Ph) and previously prepared (R = 2,4,6-Me(3)Ph, 2,6-(i)Pr(2)Ph, 3,5-(CF(3))(2)Ph) symmetrical diamidosilyl ether ligand precursors {[RNHSiMe(2)](2)O} with 2 equiv of nBuLi in THF resulted in a new class of mixed-donor amido-amino-siloxo ligands of the form {RNLiSiMe(2)N(R)SiMe(2)OLi} (R= propyl (1c), 3,5-Me(2)Ph (2c), 2,4,6-Me(3)Ph (3c), 2,6-(i)Pr(2)Ph (4c), 3,5-(CF(3))(2)Ph (5c)) in one-step and high yield via a retro-Brook-type rearrangement mechanism. Ligands 1c, 3c, and 4c have been structurally characterized in the presence and absence of THF/ether donor solvents and exhibited a range of aggregated structures with ring-laddering, ring-stacking, and cubane motifs; higher-nuclearity clusters for base-free systems were observed for 1c and 4c. 1H, (7)Li, and selected (13)C{(1)H} NMR spectra in THF-d(8) and toluene-d(8) are described; the (7)Li data are indicative of intramolecular fluxional behavior as a function of temperature but do not shed light on the nuclearity of the salts in solution.