Structural organization and dimensionality at the hands of weak intermolecular Au⋯Au, Au⋯X and X⋯X (X = Cl, Br, I) interactions

Ovens, Jeffrey S.; Truong, Kimberley N.; Leznoff, Daniel B.

doi:10.1039/c1dt11741f

Cited by 33 publications

(28 citation statements)

References 65 publications

(40 reference statements)

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“…The strength of aurophilicity is commonly associated with the relativistic effects, which are stronger for gold than for most of the other heavy metals. [30][31][32][33] However, such compounds, especially those with unsupported aurophilic interactions, are still rather rare. However, in the mid-2000 th it was proved theoretically that Au III can also favour an aurophilic attraction.…”

Section: Introductionmentioning

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: Introductionmentioning

confidence: 99%

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

et al. 2015

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“…(Figure 9(a)). 69,75,76,92,93 Uncoordinated dioxane moieties are present between these sheets, and are hydrogen bonded to H 2 O units, creating the overall 3-D network shown in Figure 9b.…”

Section: Chemistry Of Materialsmentioning

confidence: 97%

Raman Detected Sensing of Volatile Organic Compounds by Vapochromic Cu[AuX₂(CN)₂]₂ (X = Cl, Br) Coordination Polymer Materials

Ovens

Leznoff

2015

Chem. Mater.

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Two vapochromic coordination polymers Cu-[AuX 2 (CN) 2 ] 2 (X = Cl, 1; X = Br, 2) were prepared and spectroscopically characterized. Exposure of these solid materials to the volatile organic compounds dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, 1,4-dioxane, and ethylene glycol (glycol) resulted in distinct color, and IR and Raman changes. The thermal stability of the analyte-bound materials was assessed by thermogravimetric a n a l y s i s . S i n g l e -c r y s t a l s t r u c t u r e s o f C u -(analyte) 4 [AuX 2 (CN) 2 ] 2 (analyte = DMF, DMSO; X = Cl, Br) revealed an isostructural set of 1-D coordination polymer chains, where the analyte molecules were equatorially Obound to the Cu(II) centers while axially bound [AuX 2 (CN) 2 ] − units bridged these Cu(II) centers, while Cu(glycol) 4 [AuBr 2 (CN) 2 ] 2 is molecular, with monodentate glycol units. The structure of Cu 2 (OH 2 ) 4 [AuCl 2 (CN) 2 ] 4 ·4dioxane is a 2-D coordination polymer network with H 2 O-bridged Cu(II) centers and dioxane units hydrogen bonded between the 2-D sheets. The intense Raman v CN stretches for 1, 2, and their adducts form distinct, signature patterns. These "antenna" Raman v CN stretches are an effective means for sensing VOCs, and their characteristic patterns can be used to identify the VOC being detected. ■ INTRODUCTIONOver the past decade, coordination polymers have been receiving increased attention due to the ability to tailor them toward various properties such as magnetism, 1−6 porosity, 7−12 luminescence, 13−18 and vapochromism 19−25 through the strategic choice of metal centers and bridging and ancillary ligands. 26−31 More recently, coordination polymers have been explored as solid-state sensors for the detection of explosive materials 32−34 and volatile organic compounds (VOCs) in industrial settings. 16,24,25,35 Such devices have important applications in defense, industry, and safety and security. 36,37 Coordination polymers such as the Co 2+ /[Re 6 Q 8 (CN) 6 ] 4− -based (Q = S, Se) Prussian Blue analogues 19 can act as vapochromic sensors due to their highly visible color change upon exposure to certain VOCs. The porous metal−organic framework [(WS 4 Cu 4 )I 2 (dptz) 3 ]·3DMF (dptz = 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine; DMF = dimethylformamide) exhibits solvatochromism when immersed in solvents such as MeCN and CHCl 3 , lending it the potential to sense the presence of these small molecules in solution. 38 In another example, cyanoaurate-based coordination polymers have demonstrated high potential as VOC sensors. For example, the M[Au(CN) 2 ] 2 (M = Co, Cu) series exhibits stark color changes when exposed to a range of VOCs, 24,25 whereas the four polymorphs of Zn[Au(CN) 2 ] 2 display a significant change in luminescence in the presence of ammonia vapor. 16 Although not substantially porous, these materials bind and detect certain vapor-phase molecules due to the flexible nature of their coordination polymer frameworks. 39 Gold-containing materials in general have also been extensively employe...

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“…Complexes of metal dicyanides can be used in the preparation of semiconductor, optically and magnetically active materials [1][2][3][4][5][6][7], drugs-metabolites based on Au(I) [8], and luminescent substances [4,[9][10][11][12]. Complexes of dicyanodihalogenoaurates with various cations, which also exhibit similar properties [13][14][15], are less studied. Several Au(I) cyanide complexes [16,17] and Au(III) cyanodihalide complexes with ammonium cations [18][19][20][21] are known; information on [Cat] + [Au(CN) 2 Hlg 2 ]complexes with organoelement cations is present only in two papers [22,23].…”

Section: Doi: 101134/s1070363221110086mentioning

confidence: 99%

Synthesis and Structure of (4Fluorobenzyl)triphenylphosphonium Dicyanodihaloaurates [Ph3PCH2C6H4F-4][Au(CN)2Hlg2]

et al. 2021

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Hlg 2 ], Hlg = Cl, Br, and I, were synthesized from (4-fluorobenzyl)triphenylphosphonium chloride and potassium dicyanodihaloaurate in an aqueous medium. Structure of the compounds was characterized by IR, 1 H, 13 C{ 1 H}, and 19 F{ 1 H} NMR spectroscopy, elemental analysis, and X-ray structural analysis. The crystals of the synthesized complexes contain tetrahedral (4-fluorobenzyl)triphenylphosphonium cations and square centrosymmetric [Au(CN) 2 Hlg 2 ]anions.

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Structural organization and dimensionality at the hands of weak intermolecular Au⋯Au, Au⋯X and X⋯X (X = Cl, Br, I) interactions

Cited by 33 publications

References 65 publications

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

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

Raman Detected Sensing of Volatile Organic Compounds by Vapochromic Cu[AuX₂(CN)₂]₂ (X = Cl, Br) Coordination Polymer Materials

Synthesis and Structure of (4Fluorobenzyl)triphenylphosphonium Dicyanodihaloaurates [Ph3PCH2C6H4F-4][Au(CN)2Hlg2]

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Structural organization and dimensionality at the hands of weak intermolecular Au⋯Au, Au⋯X and X⋯X (X = Cl, Br, I) interactions

Cited by 33 publications

References 65 publications

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

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

Raman Detected Sensing of Volatile Organic Compounds by Vapochromic Cu[AuX2(CN)2]2 (X = Cl, Br) Coordination Polymer Materials

Synthesis and Structure of (4Fluorobenzyl)triphenylphosphonium Dicyanodihaloaurates [Ph3PCH2C6H4F-4][Au(CN)2Hlg2]

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Raman Detected Sensing of Volatile Organic Compounds by Vapochromic Cu[AuX₂(CN)₂]₂ (X = Cl, Br) Coordination Polymer Materials