79384-10-4Relevant articles and documents
A Novel Anionic Gold-Indium Cluster Compound: Synthesis and Molecular and Electronic Structure
Gabba?, Fran?ois P.,Chung, Sai-Cheong,Schier, Annette,Krüger, Sven,R?sch, Notker,Schmidbaur, Hubert
, p. 5699 - 5705 (1997)
The insertion of InBr into the Au - Br bond of [(Ph3P)AuBr] in tetrahydrofuran (thf) in the presence of [(CH2-PPh2)2] (dppe) leads to the formation of an orange complex [(dppe)2Au]+[(dppe)2Au3In 3Br7(thf)]-, 2. Analytical, spectroscopic, and X-ray structural investigations showed that this product is an anionic analogue of a neutral chloride complex [(dppe)2Au3In3Cl6(thf)3], 1, prepared recently. Both complexes have an Au3In3 cluster core of approximate C2v symmetry with one extremely short Au-Au bond [Au1-Au3 2.575(1) ?] as part of a quasilinear array P1- Au1- Au3-P4, suggesting the presence of a bis(phosphine) complex of the neutral Au2 molecule as part of the cluster. The third gold atom (Au2) is then assigned oxidation state +1. To gain deeper insight into the structure and bonding of this novel class of gold cluster compounds, regarding mainly the peculiar cluster geometry, the charge distribution, and the oxidation states, a series of scalar relativistic all-electron density functional (DF) calculations on model systems has been performed. As a model for 1, the neutral cluster {Au3(PH3)4[InCl2(H 2O)]3} was studied. For the examination of the geometry of complexes 1 and 2, the cluster Au3(PH3),4I3 has been considered as a further simplified model, where iodine replaces the InX2(thf) units. Experimental and calculated cluster geometries agree satisfactorily, and the formal oxidation states of the gold atoms (0 for Au1 and Au3, +1 for Au2) could be confirmed, but for the In centers no interpretable differences of the Mulliken charges were found.
Photophysical properties of organogold(i) complexes bearing a benzothiazole-2,7-fluorenyl moiety: Selection of ancillary ligand influences white light emission
Mihaly, Joseph J.,Stewart, David J.,Grusenmeyer, Tod A.,Phillips, Alexis T.,Haley, Joy E.,Zeller, Matthias,Gray, Thomas G.
supporting information, p. 15917 - 15927 (2019/11/11)
Herein we report three new gold(i) complexes with a benzothiazole-2,7-fluorenyl moiety bound through a gold-carbon σ-bond and either an N-heterocyclic carbene or organophosphine as ancillary ligands. The complexes have been characterized by NMR spectroscopy, X-ray crystallography, high resolution mass spectrometry, elemental analysis, and static and time-resolved optical spectroscopy. These compounds absorb almost strictly in the ultraviolet region and exhibit dual-luminescence following three freeze-pump-thaw cycles in toluene. The selection of the ancillary ligand significantly influences the excited-state dynamics of the complexes. The two phosphine containing complexes have similar fluorescence and phosphorescence quantum yields leading to generation of white light emission. The carbene containing complex exhibits a higher fluorescence quantum yield compared to its phosphorescence quantum yield resulting in a violet emission. Extensive photophysical characterization of these compounds suggests that the phosphine complexes undergo intersystem crossing more efficiently than the carbene complex. This is supported by a three-fold increase in luminescence lifetime, a halving in fluorescence quantum yield, and an increase in intersystem crossing efficiency by 25 percent for the phosphine complexes. Density-functional theory calculations support these observations where the energy gap between the S1 and T2 states for the carbene is roughly twice that of the phosphine complexes. To our knowledge this is the first example of single-component mononuclear gold(i) complexes exhibiting non-excimeric state white light emission, although a similar phenomenon has been realized for gold(iii) aryl compounds. Further, the triplet lifetimes of all three complexes are on the order of one ms in freeze-pump-thaw degassed toluene. These molecules also exhibit delayed fluorescence; all of the complexes display diffusion-controlled rate constants for triplet-triplet annihilation. Strong excited-state absorption is observed from the singlet and triplet excited-states in these molecules as well. The singlet states have excited-state extinction coefficients on the order of 1.5 × 105 M-1 cm-1 and the triplet states have excited-state extinction coefficients on the order of 1.0 × 105 M-1 cm-1
Isomorphism in the structural chemistry of two-coordinate adducts of diphenyl(2-formylphenyl)phosphine and triphenylphosphine with gold(I) halides
Dunstan, Samuel P.C.,Healy, Peter C.,Sobolev, Alexandre N.,Tiekink, Edward R.T.,White, Allan H.,Williams, Michael L.
, p. 253 - 259 (2014/07/08)
Single crystal X-ray structure determinations are recorded for diphenyl(2-formylphenyl)phosphine gold(I) halides [Ph2(Ph-CHO)PAuX], X = Cl, Br and I, and for redeterminations of enhanced precision for triphenylphosphine gold(I) halides [Ph3PAuX], X = Cl, Br, I, and SCN0.91Br0.09. These complexes, other than [Ph 2(Ph-CHO)PAuCl], together with a diverse array of other structures, crystallize as an isomorphous series in the orthorhombic space group P2 12121 a = 9.804(1)-11.906(3), b = 11.771(2)-12.996(3) and c = 12.871(1)-14.169(3) ?. In these complexes, introduction of the formyl group results in only minor differences between the conformations of the two phosphine ligands and the corresponding Au-P, Au-X, and Au-P-X bond lengths and angles. The crystal packings of [Ph3PAuX] for X = Cl, Br, I and of [Ph2(Ph-CHO)PAuX] for X = Br and I show that, while these structures are isomorphous, different supramolecular synthons may be present, suggesting global packing considerations are all-important rather than specific supramolecular interactions. This is borne out by the different packing found for the centrosymmetric [Ph2(Ph-CHO)PAuCl] structure. Crystallization of the mixed anion structure [Ph 3PAuSCN0.91Br0.09] in the above P2 12121 lattice rather than the P21/c lattice reported for pure [Ph3PAuSCN] suggests that co-crystallization with bromide may impose constraints on packing considerations which favor crystallization in the P212121 lattice.
