Bioactive and luminescent indole and isatin based gold(i) derivatives.

A series of luminescent monometallic [AuL(PPh3)] (1-3) and bimetallic [Au2(μ-dppe)L2] (4, 6, 8) and [Au2(μ-dppp)L2] (5, 7, 9) complexes, where L is either 4-cyano-indole, isatin, or 5,7-dimethyl-isatin, and dppe and dppp are 1,2-bis(diphenylphosphino)ethane and 1,3-bis(diphenylphosphino)propane, respectively, have been synthesised. X-ray diffraction confirmed the tendency to establish aurophillic interations for those complexes containing dppe. Luminescence studies and theoretical calculations revealed a different origin for both families, i.

Luminescent gold and silver complexes with the monophosphane 1-(PPh2)-2-Me-C2B10H10 and their conversion to gold micro- and superstructured materials.

Gold and silver complexes containing the monophosphane 1-PPh2-2-Me-l,2-C2B10H10 with different coordination numbers (2, 3) have been synthesized: [M(7,8-(PPh2)2-C2B9H10)(1-PPh2-2-Me-C2B10H10)] (M = Ag, Au) and [Au2(μ-1,n-C2B10H10)(1-PPh2-2-Me-C2B10H10)2] (n = 2, 12). Solid-state pyrolysis of [AuCl(1-PPh2-2-Me-C2B10H10)] and [Au2(μ-1,12-C2B10H10)(1-PPh2-2-Me-C2B10H10)2] in air and of solutions of [AuCl(1-PPh2-2-Me-C2B10H10)] deposited on silicon and silica at 800 °C results in single-crystal Au, confirmed by diffraction and SEM-EDS. The morphology of the pyrolytic products depends on the thermolytic conditions, and different novel 3-D superstructures or microcrystals are possible.

Structural and photophysical study on heterobimetallic complexes with d8-d10 interactions supported by carborane ligands: theoretical analysis of the emissive behaviour.

Heterobimetallic complexes of formula [M{(PPh2)2C2B9H10}(S2C2B10 H10)M'(PPh3)] (M=Pd, Pt; M'=Au, Ag, Cu) and [Ni{(PPh2)2C2B9H10}(S2C2B10H10)Au(PPh3)] were obtained from the reaction of [M{(PPh2)2C2B10H10}(S2C2B10H10)] (M=Pd, Pt) with [M'(PPh3)](+) (M'=Au, Ag, Cu) or by one-pot synthesis from [(SH2C2B10H10], (PPh2 )2C2B10H10, NiCl2 ⋅6 H2 O, and [Au(PPh3)](+). They display d(8)-d(10) intermetallic interactions and emit red light in the solid state at 77 K. Theoretical studies on [M{(PPh2)2C2B9H10}(S2C2B10H10)Au(PPh3)] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)-to-"P2-M-S2" (ML') charge-transfer (LML'CT) transitions for M=Pt and to metal (M)-to-"P2-M-S2" (ML') charge-transfer (MML'CT) transitions for M=Ni, Pd.

Diselenolate- and ditellurolate-carborane gold complexes.

Gold complexes with selenolate and tellurolate carborane ligands [E2C2B10H10](2-) (E = Se, Te) have been synthesized by reaction of a freshly prepared solution of [1,2-(LiE)2C2B10H10] (E = Se, Te) with [AuClL] (L = PPh3, PPh2Me, PPh2py) in a 1 : 2 molar ratio or [Au2Cl2(P∼P)] [P∼P = dppf, 1,1'-bis(diphenylphosphano)ferrocene; dppe, 1,2-bis(diphenylphosphano)ethane; dppc, 1,2-bis(diphenylphosphano)-o-carborane] in a 1 : 1 molar ratio affording complexes [Au2(μ-1,2-E2C2B10H10)L2] or [Au2(μ-1,2-E2C2B10H10)(P∼P)], respectively. The gold(III) species PPN[Au(E2C2B10H10)2] (PPN = bis(triphenylphosphano)iminium) have been afforded by reaction of PPN[AuCl4] with [1,2-(LiE)2C2B10H10]. Complex [Au4(μ-1,2-Se2C2B10H10)2(μ-dppc)2] displays a tetranuclear structure, different from the dinuclear cyclic arrangement proposed for other complexes with diphosphanes of [Au2(μ-1,2-Se2C2B10H10)(P∼P)] stoichiometry.

Influence of the group 11 metal on the emissive properties of complexes [M{(PR2)2C2B9H10}L].

The metal atoms in group 11 complexes [M{(PR2)2C2B9H10}L] [R = Ph, (i)Pr; L = tertiary phosphane; M = Au, Ag, Cu] play an important role in the emissive properties of these compounds. The influence of the metal follows the order Au ≫ Ag ≥ Cu. The three-coordinated complexes are obtained from the reaction of [AuClL], [Ag(OTf)L], or [Cu(NO3)(PPh3)2] with the closo carborane diphosphane in refluxing ethanol.

N-Heterocyclic carbene ligands as modulators of luminescence in three-coordinate gold(I) complexes with spectacular quantum yields.

The first three-coordinate gold(I) N-heterocyclic carbene (NHC) complexes have been prepared with the nido-carborane diphosphine. The complexes are brightly luminescent and present very high quantum yield values. The carbene ligand is able to modulate the energy of the emissions and, depending upon the substituent, the luminescence changes from blue to green.

Emission tuning in dinuclear gold complexes with diphosphanes containing alkyne and/or oligophenylene spacers.

Reaction of the diphosphanes P∼P [PPh(2)(C(6)H(4))(n)PPh(2) (n = 1-5) and PPh(2)C[triple bond, length as m-dash]C(C(6)H(4))C[triple bond, length as m-dash]CPPh(2)] with [AuX(tht)] (X = Cl, C(6)F(5)) in a 1 : 2 molar ratio affords dinuclear luminescent complexes of formula [(AuX)(2)(P∼P)]. The photoemissive properties of these complexes are mainly controlled by the presence of the diphosphane ligand, specifically by the phenylene spacers of the diphosphanes. At room temperature fluorescent (IL) processes dominate the emissions, both in solution and in the solid state.

Highly emissive dinuclear complexes [Au2{μ-(PPh2)2C2B9H10}(C6F5)(PR3)] with different gold fragments coordinated to an anionic diphosphine.

Reaction of the yellow-green emitters [Au{(PPh(2))(2)C(2)B(9)H(10)}(PR(3))] with [Au(C(6)F(5))(tht)] affords orange-red emissive gold complexes [Au(2){μ-(PPh(2))(2)C(2)B(9)H(10)}(C(6)F(5))(PR(3))] which contain different neutral (PR(3)) and anionic (C(6)F(5)) auxiliary ligands and an anionic diphosphine. The resulting complexes are among the few reported in which an ortho-carborane diphosphine acts in a bridging mode, and are unique in containing not a closo- (neutral), but a nido-carborane (anionic) cluster. DFT and TDDFT calculations led to the prediction of the origin of the two first singlet-triplet transitions, which is consistent with the experimental results.

Synthesis, structural characterization, photophysical properties and theoretical analysis of gold(I) thiolate-phosphine complexes.

A series of luminescent dinuclear neutral complexes of stoichiometry [(AuSPh)(2)(PPh(2)-(C(6)H(4))(n)-PPh(2))] (n = 1, 2, 3) as well as their tetranuclear cationic derivatives [(Au(2)SPh)(2)(PPh(2)-(C(6)H(4))(n)-PPh(2))(2)](PF(6))(2) are reported. Their crystal structures have been elucidated by X-ray studies. These studies indicate that, for the dinuclear species, only when n = 1 the molecules exhibit intermolecular aurophilic interactions.

Organometallic gold complexes of carborane. Theoretical comparative analysis of ortho, meta, and para derivatives and luminescence studies.

The synthesis and X-ray analysis of complexes [(micro-1,12-C2B10H10){Au(PPh3)}2] and [(micro-1,2-C2B10H10){Au(PMe3)}2] have provided the experimental data needed to analyse two points. The first point is the use of these data to carry out a computational study with the aim of comparing the electronic structures and relative stabilities of the organometallic isomers [(micro-1,n-C2B10H10){Au(PR3)}2] (n=2, 7, 12; R=Ph, Me) with those of the parent carborane clusters ortho-, meta- and para-carborane and the influence of the monophosphine substituents. The second point is focused in the influence of the steric demand of the monophosphine in the presence or not of aurophilic interactions in the ortho derivatives [(micro-1,2-C2B10H10){Au(PR3)}2] (R=Me, Ph).