Au-P Distances Research Articles

Perhalophenyl Three-Coordinate Gold(I) Complexes as TADF Emitters: A Photophysical Study from Experimental and Computational Viewpoints.

We report the synthesis of novel perhalophenyl three-coordinated gold(I) complexes using 1,2-bis(diphenylphosphino)benzene (dppBz) as the chelating ligand and [AuR(tht)] (R = C6F5, C6Cl2F3, C6Cl5) as the perhalophenyl-gold(I) source, leading to [AuR(dppBz)] (R = C6F5 (1), C6Cl2F3 (2), C6Cl5 (3)) complexes. The solid-state structures of compounds 2 and 3 consist of discrete three-coordinated Au(I) complexes, which show a distorted trigonal planar geometry for the gold center with dissimilar Au-P distances. The distorted structural arrangement is closely related to its photophysical properties. The studied complexes display very intense emissions at room temperature (RT) and at 77 K in the solid state. Studies of the emissive properties of the complexes at different temperatures suggest that the emissions are phosphorescent at 77 K and exhibit thermally activated delayed fluorescence (TADF) at RT. First-principle calculations of the photophysical processes yielded rate constants for intersystem crossing and reverse intersystem crossing that are in excellent agreement with experimental data.

1,3-Bis(4-nitrophenyl)triazenido](triphenylphosphine)gold(I).

In the title complex, [Au(C(12)H(8)N(5)O(4))(C(18)H(15)P)], the coordination geometry about the Au(I) ion is linear, with one deprotonated 1,3-bis(4-nitrophenyl)triazenide ion, [O(2)NC(6)H(4)N=N-NC(6)H(4)NO(2)](-), acting as a monodentate ligand (two-electron donor), and one neutral triphenylphosphine molecule completing the metal coordination. The triazenide ligand is almost planar (r.m.s. deviation = 0.0767 A), with the largest interplanar angle being 11.6 (7) degrees between the phenyl ring of one of the terminal 4-nitrophenyl substituents and the plane defined by the N=N-N triad. The Au-N and Au-P distances are 2.108 (5) and 2.2524 (13) A, respectively. Pairs of molecules generated by centrosymmetry are associated into a supramolecular array via intermolecular C-H...O interactions, and N...C and N...O pi-pi interactions.

Characterization of the Luminescent, Homoleptic, Three-Coordinate, Water Soluble Au(I) Complex of Trisulfonated Triphenylphosphine (TPPTS) as the Cesium Salt, Cs8[Au(TPPTS)3].5.25 H2O

The homoleptic metal-TPPTS complex Cs8[Au(TPPTS)3].5.25 H2O has been characterized structurally. The x-ray data for the triclinic crystal, P-1, with cell constants a = 13.7003(4), b = 18.0001(6), c = 18.2817(2), α = 100.249(2), β = 99.593(2), ψ = 109.818(2) shows trigonal planar Au(I) centers coordinated by three TPPTS ligands having Au-P distances equal to 2.374(6), 2.394(5), and 2.417(5)A. The structure shows a complex network of bonding involving the Cs+ ions, the sulfate groups of the ligand, and H2O solvent molecules. The [Au(TPPTS)3]8− luminesces in the solid state and in aqueous solution with a broad emission atca 520 nm which is quenched by O2. and other small molecules. The forbidden singlet to triplet absorption atca 552 nm with e≈ 0.8Lmol−1 cm−1 is also observed.

Kinetic Investigation of Homogeneous H(2)-D(2) Equilibration Catalyzed by Pt-Au Cluster Compounds. Characterization of the Cluster [(H)Pt(AuPPh(3))(9)](NO(3))(2).

The new Pt-Au hydrido cluster compound [(H)Pt(AuPPh(3))(9)](NO(3))(2) (3) has been synthesized and characterized by NMR, FABMS, and single-crystal X-ray diffraction [triclinic, P&onemacr;, a = 17.0452(1) Å, b = 17.4045(2) Å, c = 55.2353(1) Å, alpha = 89.891(1) degrees, beta = 85.287(1) degrees, gamma = 75.173(1) degrees, V = 15784.0(2) Å(3), Z = 4 (two molecules in asymmetric unit), residual R = 0.089 for 45 929 observed reflections and 3367 variables, Mo Kalpha radiation]. The Pt(AuP)(9) core geometry is a distorted icosahedron with three vertices vacant. The Pt-Au, Au-Au, and Au-P distances are within the normal ranges observed in other Pt-Au clusters. This cluster is a catalyst for H(2)-D(2) equilibration in homogeneous solution phase and has been used in a general mechanistic study of this reaction catalyzed by Pt-Au clusters. We previously proposed that a key step in the mechanism for catalytic H(2)-D(2) equilibration is the dissociation of a PPh(3) ligand to give a cluster with an open Au site for bonding of H(2) or D(2). This was based on qualitative observations that PPh(3) inhibited the rate of HD production with [Pt(AuPPh(3))(8)](NO(3))(2) (1) as catalyst. In order to test this hypothesis, phosphine inhibition (on the rate of HD production) and phosphine ligand exchange kinetic experiments were carried out with [(H)(PPh(3))Pt(AuPPh(3))(7)](NO(3))(2) (2) and 3. In this paper we show that the rate constant for phosphine dissociation determined from the PPh(3) inhibition rate study of H(2)-D(2) equilibration with cluster 2 is nearly identical to the rate constant for dissociative phosphine ligand exchange. The slower rate for H(2)-D(2) equilibration observed with 3 compared with 2 (5.5 x 10(-3) vs 7.7 x 10(-2) turnover s(-1)) is explained by its smaller rate constant for phosphine dissociation (2.8 x 10(-5) vs 2.9 x 10(-4) s(-1)). The fact that clusters 2 and 3 show similar kinetic behaviors suggests that the PPh(3) dissociation step in the catalytic H(2)-D(2) equilibration is general for 18-electron hydrido Pt-AuPPh(3) clusters.

Bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato-S,S')gold(III), [Au{P(C2H5)3}2][Au(S2C6H4)2

The structure of the title compound consists of [Au(PEt 3 ) 2 ] + cation and [Au(S 2 C 6 H 4 ) 2 ] − anion pairs. The gold(I) cations exhibit linear coordination to two PEt 3 ligands. The geometry of the gold(III) anions is square planar with four S atoms coordinated to the Au center. Typical Au-S and Au-P distances are observed

Au2(C6H5CS2)(μ-dppm)2]Cl

Bis[μ-bis(diphenylphosphino)methane-1κP:2κP'](dithiobenzoato-1κS)digold(I) chloride, [Au 2 (C 6 H 5 -CS 2 )(μ-dppm),]Cl, where dppm=C 25 H 22 P 2 , was synthesized and structurally characterized. The Au...Au separation is 3.0176 (5) A. The coordination geometries of the two Au centers differ. The bonds across the Aul center are nearly linear with Au-P distances of 2.301 (2) and 2.305 (2) A. The coordination number of the Au2 center is four; the two Au-P distances are 2.317 (2) and 2.335 (2) A and the Au-S distance is 2.718 (3) A. The dithiobenzoate ligand is coordinated to only one metal center (Au2) through one of its S atoms. The two S-C distances in this ligand are equal

The monoclinic phase [Au2(C25H22P2)2]Cl2.2CH3CN

Bis[μ-bis(diphenylphosphino)methane-P,P']digold(I) dichloride bis(acetonitrile) solvate, [Au 2 (C 25 H 22 P 2 ) 2 ]Cl 2 .2CH 3 CN, crystallized in the monoclinic system. A crystallographic inversion centre lies at the centre of the molecule. The Au-P distances are 2.299 (3) and 2.332 (3) A. The Au...Cl distance is 2.951 (4) A and the Au...Au separation is 2.994 (1) A. The molecular structure is similar to the previously reported triclinic structure except that a longer Au...Cl distance is observed for the present monoclinic structure

Bis(tri-n-butylphosphino)gold(I) tetraphenylborate

The Au atom is linearly coordinated to two disordered tri-n-butylphosphine ligands with Au-P distances of 2.310 (3) and 2.305 (4) A and a P-Au-P bond angle of 176.1 (1) o

Structure of [Au(PPh3)2][C(CN)3

Bis(triphenylphosphine)gold(1) tricyanomethanide, [Au(PPh 3 ) 2 ][C(CN) 3 ] or Au(PPh 3 ) 2 (TCM), has been synthesized and its structure determined. The Au-P distances are 2.290 (2) and 2.300 (2) A. One TCM N atom is weakly coordinated to the Au atom with an Au-N distance of 2.726 (11) A. As a result of this weak interaction, the angle P-Au-P is 161.23 (9) o rather than linear (180 o ). The geometry of TCM is trigonal planar (D 3h ) with average C-N and C-C distances of 1.14 (2) and 1.40 (2) A respectively

Structure of chlorobis(dicyclohexylphenylphosphine)gold(I).

[AuCl[C6H11)2(C6H5)P]2], Mr = 781.2, monoclinic, P2(1), a = 11.117 (4), b = 13.606 (5), c = 12.284 (4) A, beta = 109.59 (3) degrees, V = 1753 (2) A3, Z = 2, D chi = 1.48 g cm-3, lambda(Mo K alpha) = 0.71073 A, mu = 43.8 cm-1, F(000) = 792, T = 296 K, final R = 0.024 for 3239 unique observed reflections. The formation of complexes of the type LnAuX, where L is a phosphine, and X is halide or pseudohalide, shows considerable dependence on the nature of the phosphine. When L = Ph3P, three- and four-coordinated complexes are very easily prepared. However, for L = Cy3P, only linearly coordinated complexes could be isolated. The geometry of the title complex, with L = CyPhP, is best described as distorted trigonal planar. The P-Au-P angle is 158.24 (5) degrees while the P-Au-Cl angles are 92.63 (6) and 108.71 (6) degrees. Au-P distances are 2.300 (1) and 2.324 (1) A while Au-Cl is 2.744 (2) A.