Synthesis and Crystal Structure of Cyano(trimethylphosphine)gold(I).

Ahrland, Sten; Aurivillius, Bengt; Dreisch, Klaus; Norén, Bertil; Oskarsson, Åke; Carcanague, Daniel R.; Chao, Ito; Houk, K. N.

doi:10.3891/acta.chem.scand.46-0262

Cited by 37 publications

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“…Both ions associate through gold-gold contacts to form an infinite linear one-dimensional chain [77]. Neutral units [Au(CN)(PMe 3 )] aggregate to build chains [78] and the salts of the [Au(CN) 2 ] À anion display different structural features and luminescent properties, depending on the cation [79][80][81].…”

Section: Formation Of Infinite Chains and Supramolecular Arraysmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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This chapter focuses mainly on closed shell gold(I) atoms which are found to feel attraction among themselves. This attraction is able to modify expected geometries or support one-, two-or three-dimensional arrays and also leads to interesting properties. Closed shell metal cations are expected to repel each other. Nevertheless, an important number of examples containing [d 8 -d 10 -s 2 ] interactions are known. Particularly strong evidence has been accumulated on the attraction between two or more d 10 shells. In the case of gold(I) such attraction between two or more monovalent gold(I) ions in compounds has been observed structurally for a long time. In these situations the gold centers approach each other to a distance of between 2.7 and 3.3 Å. This range includes the distance between gold atoms in gold metal and approaches, or even overlaps with the range of distances found in the few real Au-Au single bonds. Schmidbaur coined the name aurophilic attraction in 1990 and defined it as the unprecedented affinity between gold atoms even with closed-shell electronic configurations and equivalent electrical charges [1]. Since that moment, aurophilicity has become one of the hot topics in gold chemistry, at first with the aim of understanding such interaction, more recently because of the observation that it may play an important role in interesting properties, thus understanding and modulating aurophilic interactions could help to govern these properties, which include the optical behavior. Although different origins are possible for the luminescent emissions of coordination complexes, such as intraligand transitions (ILT), ligand to metal or metal to ligand charge transfer transitions (LMCT, MLCT) and metal centered (MCT) transitions, in many luminescent gold complexes the emissions have been related to the presence of aurophilic interactions.Information about aurophilicity and chemical situations in which it is observed may be found in different works that may be classified as those which analyse closed shell interactions in general [2], those focused on aurophilicity [1,3], and others which analyze the role of these interactions in coordination [4] and organometallic gold Modern Supramolecular Gold Chemistry: Gold-Metal Interactions and Applications. Edited by Antonio Laguna

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Section: Formation Of Infinite Chains and Supramolecular Arraysmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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“…This is true for compounds like (C4H8S)AuBr, with a rather flat tetrahydrothiophene ligand [31], which crystallizes as [C4H8S)2Au]+ AuBr2 -with Au. Au contacts between cations and anions as they are stacked.…”

Section: Unsupported Au • •Au Contacts Between Small Moleculesmentioning

confidence: 99%

The fascinating implications of new results in gold chemistry

1990

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“…5 In this paper wherein the sterically undemanding TPA 6 ligand is used, it is shown that the state of aurophilic aggregation observed also depends on thermodynamic crystallization factors such as solvent incorporation, ionic lattice forces, and H-bonding of the ligand. Eisenberg and coworkers 7 However, its analogue, Me 3 -PAuCN, is structurally similar 9 to the species (TPA)AuCl, 2, which contains no lattice solvent molecules. This latter compound is structurally different 6a from solvent-containing (TPA)AuCl‚CH 3 CN and the protonated, H-bonded species (TPA-HCl)AuCl‚0.5H 2 O, both of which are crossed molecular dimers.…”

Section: Introductionmentioning

confidence: 98%

Syntheses, Structure, and Photoluminescence Properties of the 1-Dimensional Chain Compounds [(TPA)₂Au][Au(CN)₂] and (TPA)AuCl (TPA = 1,3,5-Triaza-7-phosphaadamantane)

et al. 2002

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The structures and temperature-dependent photoluminescence properties of the one-dimensional compounds [(TPA)(2)Au][Au(CN)(2)], 1, and (TPA)AuCl, 2, are reported. An extended linear chain with weak Au.Au interactions along the c-axis is evident in the structure of 1, and a helical chain with a pitch of 3.271 A is seen for 2. The intrachain Au...Au separation is 3.457(1) and 3.396(2) A in 1 and 2, respectively. As a result of this weak Au...Au interaction, the physical properties of these compounds are anisotropic. Scanning electron microscopy (SEM) studies indicate that single crystals of both compounds are noninsulating. Single crystals of 1 do not luminesce visibly, but grinding the crystals finely initiates a strong green emission under UV irradiation at room temperature. Further interesting optical properties include the dependence of the emission profile of the powder on the exciting wavelength and luminescence thermochromism. When excited at wavelengths < 360 nm, the powder exhibits a blue emission at 425 nm while excitation with longer wavelengths leads to a green emission near 500 nm. While the green emission dominates at ambient temperature, cooling to cryogenic temperatures leads to the dominance of the blue emission. Fibers of 2 are luminescent at 78 K with an emission band centered at 580 nm. Compound 1 crystallizes in the orthorhombic space group Cccm (No. 66), with Z = 2, a = 6.011(1) A, b = 23.877(6) A, c = 6.914(1) A, V = 992.3(3) A(3), and R = 0.0337. Compound 2 crystallizes in the trigonal space group R3 (No. 148), with Z = 18, a = 22.587(2) A, b = 22.587(2) A, c = 9.814(2) A, V = 4336 A(3), and R = 0.0283.

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Synthesis and Crystal Structure of Cyano(trimethylphosphine)gold(I).

Cited by 37 publications

References 0 publications

Gold–Gold Interactions

Gold–Gold Interactions

The fascinating implications of new results in gold chemistry

Syntheses, Structure, and Photoluminescence Properties of the 1-Dimensional Chain Compounds [(TPA)₂Au][Au(CN)₂] and (TPA)AuCl (TPA = 1,3,5-Triaza-7-phosphaadamantane)

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Synthesis and Crystal Structure of Cyano(trimethylphosphine)gold(I).

Cited by 37 publications

References 0 publications

Gold–Gold Interactions

Gold–Gold Interactions

The fascinating implications of new results in gold chemistry

Syntheses, Structure, and Photoluminescence Properties of the 1-Dimensional Chain Compounds [(TPA)2Au][Au(CN)2] and (TPA)AuCl (TPA = 1,3,5-Triaza-7-phosphaadamantane)

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Syntheses, Structure, and Photoluminescence Properties of the 1-Dimensional Chain Compounds [(TPA)₂Au][Au(CN)₂] and (TPA)AuCl (TPA = 1,3,5-Triaza-7-phosphaadamantane)