Polymorphism and luminescent behavior of linear, two-coordinate gold(i) complexes

Balch, Alan L.

doi:10.1007/bf03215516

Cited by 71 publications

(56 citation statements)

References 32 publications

(27 reference statements)

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“…Synthesis of complexes [1][2][3][4][5][6][7][8] Two general synthetic approaches to gold(III) double salts are known. The first one is a metathesis reaction between the salts of gold-containing cations and anions (Scheme 1, route A).…”

Section: Resultsmentioning

confidence: 99%

Weak aurophilic interactions in a series of Au(iii) double salts

et al. 2015

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In this work, several new examples of rare Au(III)Au(III) aurophilic contacts are reported. A series of gold(iii) double salts and complexes, viz. [AuX2(L)][AuX4] (L = 2,2'-bipyridyl, X = Cl , Br ; L = 2,2'-bipyrimidine, X = Cl , Br ; L = 2,2'-dipyridylamine, X = Cl , Br ), [AuX3(biq)] (biq = 2,2'-biquinoline, X = Cl , Br ), [LH][AuX4] (L = 2,2'-bipyridyl, X = Cl ; L = 2,2'-bipyrimidine, X = Cl ; L = 2,2'-dipyridylamine, X = Cl , Br ; L = 2,2'-biquinoline, X = Cl , Br ), [AuBr2(bpy)]2[AuBr4][AuBr2] , [AuCl2(bpm)][AuCl2] , (bpmH)2[AuBr4][AuBr2] , and (dpaH)[AuBr2] (, , and were reported earlier) was synthesized by coordination of a particular ligand to the Au(III) center and subsequent reduction of the formed product with acetone. Inspection of the X-ray structural data for , , and indicates that the Au(III) metal centers approach each other closer than the sum of their van der Waals radii, thus forming the aurophilic contacts, which were confirmed by topological charge density analysis according to the Quantum Theory of Atoms in Molecules (QTAIM). In , , and , such contacts are located only between the metal centers of the ion pair, whereas in , the aurophilic interactions form the cation-anion-anion array, and in , the aurophilicity exists between the gold atoms of the cations. It was also demonstrated that the interatomic distance alone is not a reliable measure of the aurophilic interactions, at least at the weakest limit of the interaction strength, and it needs to be complemented with structural analysis of the whole molecule and computational results.

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Section: Resultsmentioning

confidence: 99%

Weak aurophilic interactions in a series of Au(iii) double salts

et al. 2015

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“…On the other hand, different topologies were detected in the remaining solvents, which means that in all cases supramolecular structures were obtained and that these different It is accepted in the literature that the presence of aurophilic interactions can produce long wavelength luminescent crystals that are responsive to changes in their environment. 58,59,60 In particular, many gold crystalline complexes display solvo-or vapoluminescence that is a result of uptake solvent molecules into the solid phase.…”

Section: Analysis Of the Samples With Diferent Solvents Under Microscmentioning

confidence: 99%

Tuning supramolecular aurophilic structures: the effect of counterion, positive charge and solvent

et al. 2016

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The synthesis of the cationic gold(I) complexes [Au (C≡CC 5 These results reveal the importance of the introduction of a positive charge on the global supramolecular assemblies and how the counterion can modify also the resulting package. Interestingly, we have also proved that the aggregation of complexes 2, 3, 5and 6 is also affected by the solvent with direct influence on their absorption and emission properties and the global morphology of the aggregates.

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“…These hydrogen bonds involve the oxygen atom of a water molecule and hydrogen atoms of phenyl rings (X ¼ I) or the fluorine atoms of the anion and hydrogen atoms of methyl or phenyl groups (X ¼ PF 6 ) to afford a 3D or 2D structure, respectively. In the tetranuclear compound {[Au(Tab) 2 ][Au(CN) 2 ]} 2 CÀHÁ Á ÁAu and hydrogen interactions between the cyanide nitrogen or the Tab sulfur with hydrogen atoms of The polymorphism of [AuCl(PPh 2 Me)], which crystallizes in two different forms, dimers or trimers, as well as its luminescent behavior have been revised as part of a study of polymorphism of gold(I) dicoordinated linear gold(I) complexes [60]. Other example of trinuclear association is obtained by the reaction of [AuCl(SMe 2 )] with 2-aminopirydine, whose crystal structure consists of a þ/neutral/À organization of units (Figure 2.14).…”

Section: Tri-and Tetranuclear Associationsmentioning

confidence: 99%

“…Its structure is complicated by the formation of CÀHÁ Á ÁF hydrogen bonds [69]. The two chain polymorphs of [Au(CNC 6 H 11 ) 2 ]PF 6 , as well as their luminescent behavior have also been analyzed [60]. Upon protonation of [Au 3 [70].…”

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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Polymorphism and luminescent behavior of linear, two-coordinate gold(i) complexes

Cited by 71 publications

References 32 publications

Weak aurophilic interactions in a series of Au(iii) double salts

Weak aurophilic interactions in a series of Au(iii) double salts

Tuning supramolecular aurophilic structures: the effect of counterion, positive charge and solvent

Gold–Gold Interactions

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