A solid state highly emissive Cu(i) metallacycle: promotion of cuprophilic interactions at the excited states.

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.

Ruthenium(II) complexes in polymerised bicontinuous microemulsions.

Novel polymerised bicontinuous microemulsions can provide unique microenvironments for some functional molecules of scientific interests and practical applications.

Novel boxlike dinuclear or chain polymeric silver(I) complexes with polypyridyl bridging ligands: syntheses, crystal structures, and spectroscopic and electrochemical properties.

The syntheses, characterization, crystal structures, and photophysical and electrochemical properties of two dinuclear and two polymeric Ag(I) complexes with three polypyridyl ligands, 2,3-di-2-pyridylquinoxaline (L(1)), 2,3-di-2-pyridyl-5,8-dimethoxyquinoxaline (L(2)), and 2,3,7,8-tetrakis(2-pyridyl)pyrazino[2,3-g] quinoxaline (L(3)), are described. The structures of the two boxlike dinuclear complexes with L(1) and L(2) and two chemically the same but differently crystallized one-dimensional zigzag chain coordination polymers also consisting of boxlike dinuclear subunits have been elucidated by X-ray analysis. [AgL(1)(CH(3)CN)](2)-(BF(4))(2).2CHCl(3) (1): monoclinic, C2/c; a = 28.631(2), b = 12.2259(11), c = 14.3058(12) A; beta = 99.180(2) degrees; Z = 4. [AgL(2)(CH(3)CN)(2)](2)(ClO(4))(2) (2): triclinic, P1; a = 12.3398(2), b = 13.750(2), c = 14.326(7) A; alpha = 83.494(3), beta = 74.631(3), gamma = 76.422(3) degrees; Z = 4. [[Ag(2)L(3)(NO(3))(2)].CH(3)CN](infinity) (3a): monoclinic, P2(1)/c; a = 9.5836(8), b = 13.4691(12), c = 14.0423(12) A; beta = 107.753(2) degrees; Z = 4. [Ag(2)L(3)()(NO(3))(2)](infinity) (3b): monoclinic, P2(1)/c; a = 8.4689(6), b = 16.0447(12), c = 11.7307(8) A; beta = 102.051(1) degrees; Z = 2. The structures of the dinuclear complexes 1 and 2 are similar to each other, with the two intramolecular Ag(I) centers of each complex being spanned by two ligands thus forming a unique boxlike cyclic dimer. In 1, each Ag(I) center is four-coordinated by three nitrogen atoms of two L(1) ligands and a CH(3)CN nitrogen donor, taking a distorted tetrahedral coordination geometry. The coordination environment of Ag(I) in 2 is similar to that in 1, except the formation of an additional weak coordination bond with the oxygen atom of the methoxy group of L(2). The structures of 3a,b are very similar to each other, except for the stacking patterns in the crystal lattices, and the cyclic boxlike dinuclear unit, which is similar to the structure of 1, constitutes the fundamental building block to form the one-dimensional zigzag chain structures due to the "end-on" nature of L(3). 1-3 exhibit metal-perturbed intraligand transitions in solution in 360-390 nm regions. Cyclic voltammetric studies of these complexes show the presence of reduction peak at approximately -0.5 V vs Fc(+/0). In the solid state at 77 K, they exhibit broad emission that may be assignable to originate from the metal-perturbed intraligand transitions.

Synthesis, characterization, Langmuir-Blodgett film-forming properties, and second-harmonic-generation studies of ruthenium(II) complexes with long hydrocarbon chains.

Several ruthenium(II) surfactants of general formula [Ru(bpy)(2)L](2+) [L = N-(2-pyridylmethylene)-3,4-bis(tetradecyloxy)benzenamine, N-(2-pyridylmethylene)-3,4-bis(octadecyloxy)benzenamine, 9-(3,4-bis(tetradecyloxy)benzenamino)-4,5-diazafluorene, 9-(4-(tetradecyloxy)-4'-azabenzenamino)-4,5-diazafluorene, 4,7-dinonadecyl-1,10-phenanthroline] and [Ru(L)(3)](2+) (L = 4,7-dinonadecyl-1,10-phenanthroline) were synthesized and characterized by elemental analysis, (1)H NMR, UV-vis, luminescence spectroscopy, and cyclic voltammetry. Their Langmuir-Blodgett (LB) film formation properties and surface pressure-area (pi-A) isotherms were also studied. Two complexes were found to show second-harmonic-generation (SHG) behavior.

Syntheses, photophysics, and photochemistry of trinuclear copper(I) thiolate and hexanuclear copper(I) selenolate complexes: X-ray crystal structures of [Cu(6)(mu-dppm)4(mu(3)-SePh)4](BF(4))2 and [Cu(6)(mu-(Ph(2)P)(2)NH(4))(mu(3)-SePh)4](BF(4)2.

A series of trinuclear copper(I) thiolate complexes, [Cu(3)(mu-dppm)(3)(mu(3)-SR)(2)]BF(4) (R = C(6)H(4)Cl-4, C(6)H(4)CH(3)-4, C(6)H(4)OCH(3)-4, C(6)H(4)(OCH(3))(2)-3,4, C(6)H(4)-benzo-15-crown-5, or (t)()Bu), [Cu(3)(mu-dppm)(3)(mu(3)-S(t)()Bu)](BF(4))(2), and [Cu(3)(mu-dppm)(3)(mu(3)-SR)(mu(3)-Cl)]BF(4) (R = C(6)H(4)CH(3)-4, C(6)H(4)(t)()Bu-4, or C(6)H(4)(CH(3))(3)-2,4,6) and two hexanuclear copper(I) selenolate complexes, [Cu(6)(mu-P(wedge)P)(4)(mu(3)-SePh)(4)](BF(4))(2) (P(wedge)P = dppm, (Ph(2)P)(2)NH), have been synthesized, and their photophysical properties have been studied. The X-ray crystal structures of both copper(I) selenolate complexes have been determined. These complexes have been shown to exhibit long-lived low-energy emission in solution, attributed to an excited state of predominantly ligand-to-metal charge-transfer [chalcogenolate to copper(I)] origin.

Synthesis, structural characterization, and photophysics of dinuclear gold(II) complexes [(Au(dppn)Br)(2)](PF(6))(2) and [(Au(dppn)I)(2)](PF(6))(2) with an unsupported Au(II)-Au(II) Bond.

A series of novel dinuclear gold(II) complexes having an unsupported Au(II)-Au(II) bond with well-defined oxidation state at the gold center were synthesized. Red shifts in both the low-energy absorption and emission bands were observed upon increasing the donor ability of the coordinated halogen atoms.

Synthesis, emission, and electrochemical properties of luminescent dinuclear zinc(II) chalcogenolate complexes. Dynamic 1H NMR studies and X-ray crystal structure of [(bpy)Zn2(SC6H4-Cl-p)(mu-SC6H4-Cl-p)(mu-OAc)2].

A series of novel luminescent dinuclear zinc(II) diimine complexes with bridging chalcogenolate ligands have been synthesized, in which the two zinc atoms were found to exist in different coordination environment. The luminescence and electrochemical behavior of these complexes have been studied. These complexes have also been shown to exhibit dynamic fluxional behavior in solution due to an exchange of the bridging and terminal thiolate ligands. The mechanism and kinetics of which have been investigated by variable-temperature 1H NMR studies. The X-ray crystal structure of [(bpy)Zn2(SC6H4-Cl-p)(mu-SC6H4-Cl-p)(mu-OAc)2] has also been determined.

Electronic and resonance Raman spectra of [Au2(CS3)2]2-. Spectroscopic properties of a "short" Au(I)-Au(I) bond.

The anion [Au2(CS3)2]2- has an unusually short Au-Au distance (2.80 A) for a binuclear Au(I) complex. We report detailed Raman studies of the nBu4N+ salt of this complex, including FT-Raman of the solid and UV/vis resonance Raman of dimethyl sulfoxide solutions. All five totally symmetric vibrations of the anion have been located and assigned. A band at delta nu = 125 cm-1 is assigned to nu (Au2). The visible-region electronic absorption bands (384 (epsilon 30,680) and 472 nm (epsilon 610 M-1 cm-1)) are attributable to CS3(2-) localized transitions, as confirmed by the dominance of nu sym(C-Sexo) (delta nu = 951 cm-1) in RR spectra measured in this region. An absorption band at 314 nm (22,250 M-1 cm-1) is assigned as the metal-metal 1(d sigma*-->p sigma) transition, largely because nu sym(C-Sexo) is not strongly enhanced in RR involving this band. Observation of the expected strong resonance enhancement of nu (Au2) was precluded as a result of masking by intense solvent Rayleigh scattering in the UV.