Luminescence of cesium dicyanoaurate(I). Evidence for extended Au(I)Au(I) interactions in two dimensions

Markert, J. T.; Blom, Nils; Roper, Gerald C.; Perregaux, A.; Nagasundaram, N.; Corson, Michael R.; Lüdi, A.; Nagle, Jeffrey K.; Patterson, Howard H.

doi:10.1016/0009-2614(85)85311-2

Cited by 31 publications

(18 citation statements)

References 24 publications

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“…The concentration dependence of the red shift of the absorption edge of [Au(CN) 2 ] − in solution64 is consistent with the orbital perturbation brought about by the Au⋅⋅⋅Au contacts. A similar interpretation can be given to the different luminescence65, 66 of the Cs + and K + salts of [Au(CN) 2 ] − : while the former presents two contacts per Au atom at 3.11 Å and luminescences at λ = 458 nm, the latter has four contacts per metal at a much longer distance (3.64 Å) and the luminescence appears at λ = 390 nm. For more reports on the decreased energy of the luminescence of dicyanoaurate in the solid state, see the references cited by Rawashdeh‐Omary et al64…”

Section: Introductionsupporting

confidence: 63%

The Nature of Intermolecular Cu^I⋅⋅⋅Cu^IInteractions: A Combined Theoretical and Structural Database Analysis

Carvajal¹,

Álvarez²,

Novoa³

2004

Chemistry A European J

142

126

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The nature of intermolecular interactions between dicoordinate Cu(I) ions is analyzed by means of combined theoretical and structural database studies. Energetically stable Cu(I).Cu(I) interactions are only found when the two monomers involved in the interaction are neutral or carry opposite charges, thus allowing us to speak of bonding between the components of the bimolecular aggregate. A perturbative evaluation of the components of the intermolecular interaction energies, by means the IMPT scheme of Stone, indicates that both the Coulombic and dispersion forces are important in determining the Cu(I).Cu(I) bonding interactions, because only a small part of that energy is attributable to Cu.Cu interactions, while a large component results from Cu.ligand interactions. The electrostatic component is the dominant one by far in the interaction between charged monomers, while in the interaction between neutral complexes, the electrostatic component is found to be of the same order of magnitude as the dispersion term. Bimolecular aggregates that have like charges are repulsive by themselves, and their presence in the solid state results from anion.cation interactions with ions external to this aggregate. In these cases, the short-contact Cu.Cu interactions here should be more properly called counterion-mediated Cu.Cu bonds.

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Section: Introductionsupporting

confidence: 63%

The Nature of Intermolecular Cu^I⋅⋅⋅Cu^IInteractions: A Combined Theoretical and Structural Database Analysis

Carvajal¹,

Álvarez²,

Novoa³

2004

Chemistry A European J

142

126

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“…[96] Already in many publications of early structural work it has repeatedly been assumed that "there may be significant bonding interactions among the gold atoms in these solids". [97] Such "low-dimensional Au•••Au interactions"h ave also been held responsible for the unusual absorption and emission characteristics of alkali dicyanoaurates(I) under high pressures (20 kbar). Extreme red-shifts of the emission were observed, which are among the largest known for solid-state compounds.…”

Section: The Case Of the Dicyanoaurate(i) Anionmentioning

confidence: 99%

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Schmidbaur

Raubenheimer

2020

Angew Chem Int Ed

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Excimers and exciplexes are defined as assemblies of atoms or molecules A/A′ where interatomic/intermolecular bonding appears only in excited states such as [A2]* (for excimers) and [AA′]* (for exciplexes). Their formation has become widely known because of their role in gas‐phase laser technologies, but their significance in general chemistry terms has been given little attention. Recent investigations in gold chemistry have opened up a new field of excimer and exciplex chemistry that relies largely on the preorganization of gold(I) compounds (electronic configuration AuI(5d10)) through aurophilic contacts. In the corresponding excimers, a new type of Au⋅⋅⋅Au bonding arises, with bond energies and lengths approaching those of ground‐state Au−Au bonds between metal atoms in the Au0(5d106s1) and AuII(5d9) configurations. Excimer formation gives rise to a broad range of photophysical effects, for which some of the relaxation dynamics have recently been clarified. Excimers have also been shown to play an important role in photoredox binuclear gold catalysis.

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“…The luminescence of many gold complexes has attracted considerable attention. − Recent work on the luminescent behavior of monomeric, linear complexes of the type (Ph 3 E)AuX (where E is P or As and X is Cl or Br) in the solid state has demonstrated that dual phosphorescences from two excited states occur . The high-energy emission which has its origin at 360 nm has been assigned to an intraligand phosphorescence that results from a phenyl-localized 3 ππ* state.…”

Section: Introductionmentioning

confidence: 99%

Solid State Structures and Gold−Gold Bonding in Luminescent Halo(dimethylphenylphosphine)gold(I) Complexes

et al. 1996

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The structures of the series of two-coordinate gold(I) complexes {(Me(2)PhP)AuX}(n) where X is Cl, Br, or I have been examined by X-ray diffraction. The chloro complex crystallized in two separate polymorphic forms. Colorless hexagonal blocks of {(Me(2)PhP)AuCl}(3) crystallized in the monoclinic space group P2(1)/m with a = 12.141(4) Å, b = 8.433(2) Å, c = 14.834(3) Å, and beta = 94.15(2) degrees at 130 K with Z = 2. Refinement of 2837 reflections and 177 parameters yielded R = 0.066 and R(w) = 0.069. The complex consists of three nearly linear P-Au-Cl units that are connected by Au-Au contacts at 3.091(2) and 3.120(2) Å. Colorless prisms of {(Me(2)PhP)AuCl}(2) form in the orthorhombic space group P2(1)2(1)2(1) as described earlier (Cookson, P. D.; Tiekink, E. R. T. Acta Crystallogr. 1993, C49, 1602). The two nearly linear P-Au-Cl units are staggered and connected through a Au-Au bond (3.230(2) Å). Colorless rectangular prisms of {(Me(2)PhP)AuBr}(2) form in the monoclinic space group P2(1) with a = 9.572(5) Å, b = 8.757(3), and c = 12.915(7) at 130 K with Z = 2. Refinement of 2469 reflections with 118 parameters yielded R = 0.080 and R(w) = 0.084. {(Me(2)PhP)AuI}(2) is isomorphous with the bromo complex with a = 9.736(2) Å, b = 8.890(2) Å, and c = 13.160(5) Å at 130 K with Z = 2. Refinement of 2796 reflections with 119 parameters yielded R = 0.052 and R(w) = 0.058. These complexes are similar to the chloro dimer but with altered orientations of the phenyl substituent. The predicted order of ligand effects (Cl> Br > I) on Au-Au distances from quasi-relativistic calculations is borne out in the experimental values: 3.230 Å (Cl); 3.119 Å (Br); 3.104 Å (I). In dichloromethane, these complexes dissociate into monomeric units but there is some evidence for the presence of dimers in concentrated solutions of the iodide compound.

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Luminescence of cesium dicyanoaurate(I). Evidence for extended Au(I)Au(I) interactions in two dimensions

Cited by 31 publications

References 24 publications

The Nature of Intermolecular Cu^I⋅⋅⋅Cu^IInteractions: A Combined Theoretical and Structural Database Analysis

The Nature of Intermolecular Cu^I⋅⋅⋅Cu^IInteractions: A Combined Theoretical and Structural Database Analysis

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Solid State Structures and Gold−Gold Bonding in Luminescent Halo(dimethylphenylphosphine)gold(I) Complexes

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Luminescence of cesium dicyanoaurate(I). Evidence for extended Au(I)Au(I) interactions in two dimensions

Cited by 31 publications

References 24 publications

The Nature of Intermolecular CuI⋅⋅⋅CuIInteractions: A Combined Theoretical and Structural Database Analysis

The Nature of Intermolecular CuI⋅⋅⋅CuIInteractions: A Combined Theoretical and Structural Database Analysis

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Solid State Structures and Gold−Gold Bonding in Luminescent Halo(dimethylphenylphosphine)gold(I) Complexes

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The Nature of Intermolecular Cu^I⋅⋅⋅Cu^IInteractions: A Combined Theoretical and Structural Database Analysis

The Nature of Intermolecular Cu^I⋅⋅⋅Cu^IInteractions: A Combined Theoretical and Structural Database Analysis