Abstract:A mixture of cyclic gold(I) complexes [Au(2)(μ-cis-dppen)(2)]X(2) (X = OTf 1, PF(6)3) and [Au(cis-dppen)(2)]X (X = OTf 2, PF(6)4) is obtained from the reaction of [Au(tht)(2)]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au(3)(μ-trans-dppen)(3)]X(3) (X = OTf 11, PF(6)12) and tetranuclear [Au(4)(μ-dppa)(4)]X(4) (X = OTf 13, PF(6)14… Show more
“…29,30 The formal oxidation state of each gold atom is +1, and the coordination geometry about each Au(I) center is nearly linearly with angles of 173.72(6) ° and 172.69(6)° found for the P(1)-Au(1)-Cl(1) and P(2)-Au(2)-Cl(2) linkages, respectively. The mean Au-P bond distance of 2.232 Å is similar to those Au-P distances in the diphosphine-bridged compounds Au 2 Cl 2 (-bma), 5 Au 2 I 2 (-dppen), 31 and Au 2 Cl 2 (-dppbz). 32 The torsion angles for the P(1)-Au(1)-Au(2)-P(2) and…”
“…29,30 The formal oxidation state of each gold atom is +1, and the coordination geometry about each Au(I) center is nearly linearly with angles of 173.72(6) ° and 172.69(6)° found for the P(1)-Au(1)-Cl(1) and P(2)-Au(2)-Cl(2) linkages, respectively. The mean Au-P bond distance of 2.232 Å is similar to those Au-P distances in the diphosphine-bridged compounds Au 2 Cl 2 (-bma), 5 Au 2 I 2 (-dppen), 31 and Au 2 Cl 2 (-dppbz). 32 The torsion angles for the P(1)-Au(1)-Au(2)-P(2) and…”
“…On the other hand, the core-to-exo distances are in the range 2.970 -3.072 Å, which are markedly longer than Au-Au distance in the bitetrahedral core (2.648 -2.872 Å). Other Au 6 +2Au type clusters (12 and 13) were reported recently [91,96], which show almost similar structural parameters (Table 4).…”
Synthetic techniques, geometrical structures, and electronic absorption spectra of phosphine-coordinated pure-gold molecular clusters (PGCs) accumulated over 40 years are comprehensively collected especially for those with unambiguous X-ray crystal structures available. Inspection of the electronic absorption spectra from geometrical aspects reveals that their optical properties are highly dependent on the cluster geometries rather than the nuclearity. Recent examples of unusual clusters that show unique color / photoluminescence properties and their utilization for stimuli-responsive modules are also presented.
“…The composition of the molecular orbitals and theoretical absorption spectra were plotted using the Chemissian program. 22,23 The NBO analyses were carried out on the stationary points using the NBO 3.1 program 24 as implemented in the Gaussian 03 program suite.…”
The photophysical properties of three series of cyclometalated organoplatinum(ii) complexes were studied and the influence of changing the ancillary ligands and substituents on their luminescence properties were investigated.
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