Structures and luminescent properties of polynuclear gold(I) halides containing bridging phosphine ligands

Xiao, Hong; Weng, Yu Xiang; Wong, Wing Tak; Mak, Thomas C. W.; Ming, Chi

doi:10.1039/a605911b

Cited by 75 publications

(54 citation statements)

References 18 publications

(12 reference statements)

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“…[36,38,56] The Au···Au···Au angles are 175.47(2) to 180.00(2)8; they are closer to 1808 than those of [Au 3 3 (167.21 (2)8), [36] (4)8), [39] [Au 3 -A C H T U N G T R E N N U N G (dpmp) 2 Cl 2 ]Cl·CH 2 Cl 2 (149.56 (9)8), [38] 6 ] 2 (141.12(6)-143.46(4)8; X= halide ion) [56] and [Au 4 (1)-163.89(1)8). [40] The closest gold···anion distances in the crystal structures of complexes [11,12] and in [Au 4 A C H T U N G T R E N N U N G (dpmppm) 2 ]A C H T U N G T R E N N U N G [PF 6 ] 3 (3.077 (Au···FPF 5 )).…”

Section: A C H T U N G T R E N N U N G (Dpmp) 2 ]mentioning

confidence: 98%

“…The dpmp [36][37][38] and dpmppm [40] ligands may not be ideal for spectroscopic studies as intraligand excited states of the phenyl substituents can interfere with the spectroscopic assignments. The dmmp ligand, on the other hand, was reported to form trinuclear Au I complexes with a Au···Au···Au angle of 1368.…”

Section: A C H T U N G T R E N N U N G [Nds*a C H T U N G T R E N N Umentioning

confidence: 99%

“…In literature, the available phosphine ligands for the synthesis of tri-and tetranuclear metal complexes include dpmp/dppp, [36][37][38] dmmp, [39] and dpmppm [40] (dpmp and dppp = bis(diphenylphosphinomethyl)phenylphosphine, dmmp = bis(dimethylphosphinomethyl)methylphosphine), dpmppm = bis[(diphenylphosphinomethyl)phenylphosphino]methane). The dpmp [36][37][38] and dpmppm [40] ligands may not be ideal for spectroscopic studies as intraligand excited states of the phenyl substituents can interfere with the spectroscopic assignments.…”

Section: A C H T U N G T R E N N U N G [Nds*a C H T U N G T R E N N Umentioning

confidence: 99%

“…[38] Upon excitation of 6 at 298 nm in CH 2 Cl 2 , an emission band at 327 nm with an emission quantum yield of < 0.003 is observed ( Figure 6). The excitation spectrum of this 327 nm band is the same as the corresponding absorption spectrum, suggesting that the emission comes…”

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confidence: 94%

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The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

Tong

Kui

Chao

et al. 2009

Chemistry A European J

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The complexes [Au(3)(dcmp)(2)][X](3) {dcmp=bis(dicyclohexylphosphinomethyl)cyclohexylphosphine; X=Cl(-) (1), ClO(4) (-) (2), OTf(-) (3), PF(6) (-) (4), SCN(-)(5)}, [Ag(3)(dcmp)(2)][ClO(4)](3) (6), and [Ag(3)(dcmp)(2)Cl(2)][ClO(4)] (7) were prepared and their structures were determined by X-ray crystallography. Complexes 2-4 display a high-energy emission band with lambda(max) at 442-452 nm, whereas 1 and 5 display a low-energy emission with lambda(max) at 558-634 nm in both solid state and in dichloromethane at 298 K. The former is assigned to the (3)[5dsigma*6psigma] excited state of [Au(3)(dcmp)(2)](3+), whereas the latter is attributed to an exciplex formed between the (3)[5dsigma*6psigma] excited state of [Au(3)(dcmp)(2)](3+) and the counterions. In solid state, complex [Ag(3)(dcmp)(2)][ClO(4)](3) (6) displays an intense emission band at 375 nm with a Stokes shift of approximately 7200 cm(-1) from the (1)[4dsigma*-->5psigma] absorption band at 295 nm. The 375 nm emission band is assigned to the emission directly from the (3)[4dsigma(*)5psigma] excited state of 6. Density functional theory (DFT) calculations revealed that the absorption and emission energies are inversely proportional to the number of metal ions (n) in polynuclear Au(I) and Ag(I) linear chain complexes without close metalanion contacts. The emission energies are extrapolated to be 715 and 446 nm for the infinite linear Au(I) and Ag(I) chains, respectively, at metalmetal distances of about 2.93-3.02 A. A QM/MM calculation on the model [Au(3)(dcmp)(2)Cl(2)](+) system, with Au...Cl contacts of 2.90-3.10 A, gave optimized Au...Au distances of 2.99-3.11 A in its lowest triplet excited state and the emission energies were calculated to be at approximately 600-690 nm, which are assigned to a three-coordinate Au(I) site with its spectroscopic properties affected by Au(I)...Au(I) interactions.

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Section: A C H T U N G T R E N N U N G (Dpmp) 2 ]mentioning

confidence: 98%

Section: A C H T U N G T R E N N U N G [Nds*a C H T U N G T R E N N Umentioning

confidence: 99%

Section: A C H T U N G T R E N N U N G [Nds*a C H T U N G T R E N N Umentioning

confidence: 99%

mentioning

confidence: 94%

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The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

Tong

Kui

Chao

et al. 2009

Chemistry A European J

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“…In addition, heterometallic complexes containing gold and iridium or gold and ruthenium with similar patterns, but with two different metal centers, have been described and their luminescent properties also studied. The fluxional behavior in solution of compound [Au 2 (TP) 2 ] 2þ has been studied by NMR [245,[342][343][344][345][346][347][348][349][350][351][352][353][354].…”

Section: Complexes With Bridging Bidentate Ligandsmentioning

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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Aurophilic Attraction and Luminescence of Binuclear Gold(I) Complexes with Bridging Phosphine Ligands: ab initio Study

2001

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Electronic structure and spectroscopic properties of [Au2(dpm)2]2+ (dpm = bis(diphosphino)methane) were studied by ab initio calculations. The absorption and emission spectra of this binuclear gold(I) complex in acetonitrile and in the solid state were calculated by single excitation configuration interaction (CIS) method. In the calculations, the solvent effect was taken into account by the weakly solvated [Au2(dpm)2]2+ x (MeCN)2 complex. The ground state structures of [Au2(dpm)2]2+ and [Au2(dpm)2]2+ x (MeCN)2 were optimized by the second-order Møller-Plesset perturbation (MP2) method, while the emissive triplet excited state structures were optimized by the CIS calculations. The results reveal that coordination of acetonitrile to the gold atom in the 3[d(sigma*)s(sigma)] excited state causes a significant red shift in emission energy. The weak aurophilic attraction exists in the ground states of [Au2(dpm)2]2+ and [Au2(dpm)2]2+ x (MeCN)2, and is greatly enhanced in their 3[d(sigma*)s(sigma)] excited states. In acetonitrile, the 3Au(s(sigma)) --> 1Ag(d(sigma*)) transition (phosphorescence) of [Au2(dpm)2]2+ was calculated at 557 nm, in consistent with the observed emission of [Au2(dppm)2](ClO4)2 (dppm = bis(diphenylphosphino)methane) at 575 nm. A high energy emission at 331 nm is predicted for [Au2(dpm)2]2+ in the absence of the interaction between the gold atom and solvent molecule and/or neighboring anion in the excited state. The CIS calculations on the excited states also reveal that the two absorption bands at 278 and 218 nm recorded for [Au2(dcpm)2](ClO4)2 in acetonitrile can be attributed to the 1Ag(d(sigma*)) --> 1Au(p(sigma)) and 1Ag(d(sigma*)) --> 1Au((sp)sigma) transitions, respectively.

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Structures and luminescent properties of polynuclear gold(I) halides containing bridging phosphine ligands

Cited by 75 publications

References 18 publications

The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

Gold–Gold Interactions

Aurophilic Attraction and Luminescence of Binuclear Gold(I) Complexes with Bridging Phosphine Ligands: ab initio Study

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Structures and luminescent properties of polynuclear gold(I) halides containing bridging phosphine ligands

Cited by 75 publications

References 18 publications

The 3[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

The 3[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

Gold–Gold Interactions

Aurophilic Attraction and Luminescence of Binuclear Gold(I) Complexes with Bridging Phosphine Ligands: ab initio Study

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The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands