Aurophilic Au Research Articles

Structural and vibrational spectroscopic analysis of two Au(I) − NHC carbene complexes potential anticancer agents with intramolecular aurophilic interactions: A DFT study

Structural, electronic, and vibrational spectroscopic analysis using DFT/B3LYPD with LanL2DZ and SDD basis of two novel cationic gold(I) complexes with potential anticancer application exhibiting intramolecular aurophilic Au···H–N interactions, ranging from 2.74 to 2.84 Å. Both basis sets yielded equilibrium geometries and computed IR spectra in excellent agreement with X-ray structures and experimental IR spectra data. Despite structural differences in the thione co-ligand, both cationic complexes have remarkably similar dipole moments ranging from 6.4 to 6.6 D and HOMO-LUMO energy gaps, ranging from 5.0 to 5.3 eV, indicating that both possess almost identical solubility and similar chemical stability. Solvation free energies ranging from −35.9 to −39.0 kcal/mol were calculated using the implicit solvation SMD model, suggesting solvent effects play a significant role.

Isocyanide π-Hole Interactions Supported by Aurophilic Forces

Treatment of the [AuCl(tetrahydrothiophene)] complex with 4-chloro-2-iodo-1-isocyanobenzene furnished the gold(I) compound [AuCl(CNC6H3-4-Cl-2-I)] (1). In the crystal structure of 1, the linear C–Au–Cl group is subject to the solid-state head-to-tail pairing, which is determined by the aurophilic Au⋯Au and the rare π-holeCN⋯Cl interactions. These two types of structure-determining interactions are complementary to each other, and the system of Au⋯Au and CCN⋯Cl contacts accomplishes a 2D extended ladder-type architecture. In addition, the terminal I-atoms are involved in the three-center halogen bonding. Density functional theory calculations, employing a set of computational tools, verified the role of Au⋯Au and π-holeCN⋯Cl noncovalent bonds in the spectrum of noncovalent forces.

Self-Assembled Chiral Phosphorescent Microflowers from Au Nanoclusters with Dual-Mode pH Sensing and Information Encryption.

The self-assembly of chiral metal nanoclusters into supramolecular chiral aggregates is of interest for developing advanced materials. Herein, we manipulated the self-assembly of Au nanoclusters modified by l-/d-cysteine (l-/d-AuNCs) into ordered microstructures featuring enhanced phosphorescence and optical activities. The formation of these aggregates was driven by synergistic effect of coordination and electrostatic interactions assisted by Cd2+/H+. Detailed structural characterization and theoretical studies confirmed that the compact aggregation structures are essential for the emission enhancement and the chirality amplification of l-/d-AuNCs. Interestingly, upon the formation of microflowers, the emission lifetime was prolonged to 3.34 ms with a switch from fluorescence to phosphorescence induced by aurophilic Au(I)···Au(I) interactions and intensive ligand-to-metal charge transfer (LMCT). Moreover, both the CD and photoluminescence (PL) signals of the microflowers exhibited pH-responsiveness. This dual-mode sensitive platform could be developed as a pH sensor with improved accuracy. Additionally, the pH-responsive photoluminescence ON/OFF switch of the microflowers could be employed for reliable information encryption and decryption. This study provides useful ideas for regulating the self-assembly of nanoclusters to generate desired photophysical properties with potential applications.

Chiral gold(I)-containing polymeric composites: chiroptical sensing and circularly polarized luminescence

Fiber-like gold(I)-containing polymeric composites have been constructed in water by coupling poly(ethylene glycol)-block-poly-(L-glutamic sodium) (PEGn-b-PLGSm) with cationic gold(I) complex. The resulting composites showed a gradual luminescence enhancement with increasing molecular weight of the PLGSm block, due to gradually increasing aurophilic Au(I)···Au(I) interactions in the gold(I) complex. Moreover, the chiral transfer from the chiral block copolymers to the gold(I) complex was achieved for the first time, leading to strong circularly polarized luminescence (CPL). Such chiroptical sensing offers a general approach for constructing CPL active polymer/metal complex composites.

Macrocyclic dimer of Fc(NHC(O)PPh2-AuCl)2 induced by aurophilic interactions, and chirality induction into Fc core

The reaction of 1,1′-bis(diphenylphosphinecarboxamidyl)ferrocene, Fc(NHC(O)PPh2)2 L, with chloro(tetrahydrothiophene)gold(I), [AuCl(tht)], was found to afford the macrocyclic dimer gold(I) complex, {Fc(NHC(O)PPh2-AuCl)2}21, induced by aurophilic interactions. The macrocyclic dimer gold(I) complex 1 gave needle 1needle and plate 1plate crystals. The single-crystal X-ray structure determination of 1 was demonstrated to reveal the self-association properties of the gold(I) and the phosphinecarboxamide moieties in the solid state. The macrocyclic dimer gold(I) complex 1needle crystallized in the space group C2/c with P- and M-helical chirality of the ferrocene (Fc) core. Both conformational enantiomers were found to form homochiral PP and MM macrocyclic dimers, respectively, through intermolecular aurophilic Au(I)–Au(I) interactions and hydrogen bonds between the NH of the phosphinecarboxamide moiety and the Cl of AuCl of the other molecule, wherein PP and MM macrocyclic dimers induced S- and R-conformational enantiomers based on the torsional twist about the Au(I)–Au(I) axis, respectively. The macrocyclic dimer gold(I) complex 1plate crystallized in the space group P21/c with heterochiral PM macrocyclic dimer through aurophilic Au(I)–Au(I) interactions with R- and S- conformational enantiomers. The macrocyclic dimer gold(I) complex 1 was found to bind halide ion of ammonium salt by using the phosphinecarboxamide binding sites. The addition of l-proline methyl ester hydrochloride to the solution of 1 was demonstrated to induce the P-helical chirality of the Fc core.

Electron Dose-Controlled Formation, Growth, and Assembly of Nanoclusters and Nanoparticles from Aurophilic Au(I)-Thiolate Ensemble on Surfaces.

The ability to precisely control electron irradiation-induced formation, growth, and assembly of nanoclusters or nanoparticles on a solid surface is important for design and creation of catalytically or chemically active surface sites and interfaces free from chemical reducing agents. Here, we show the results of an investigation of the electron dose-controlled formation, growth, and assembly of nanoclusters and nanoparticles in a molecularly assembled thin film of Au(I)-thiolate motifs on a substrate, highlighting an in situ monitoring of the evolution of morphology under controlled electron dose. With aurophilic motifs of Au(I)-thiolate being confined by electrostatic interactions, the sizes of Au nanoclusters and nanoparticles were shown to increase with electron dose, revealing a propensity of a string alignment of the grown nanoclusters and nanoparticles. This growth preference to one-dimensional assembly is supported by the analysis of the surface reaction kinetics in terms of the surface density of electron dose for the growth of the nanoclusters and nanoparticles. The electron dose-controlled size-focusing and directional assembly of nanoclusters and nanoparticles may be exploited as new strategy for the precise control of nanoclusters or nanoparticles and their assemblies on solid surfaces not only free from chemical reducing agent but also with the ability of visual monitoring of the morphological evolution during growth.

Copper and Gold Cyclic (Alkyl)(amino)carbene Complexes with Sub-Microsecond Photoemissions: Structure and Substituent Effects on Redox and Luminescent Properties.

Copper and gold halide and pseudo-halide complexes stabilised by methyl-, ethyl- and adamantyl-substituted cyclic (alkyl)(amino)carbene (CAAC) ligands are mostly linear monomers in the solid state, without aurophilic Au⋅⋅⋅Au interactions. (Et2 L)CuCl shows the highest photoluminescence quantum yield (PLQY) in the series, 70 %. The photoemissions of Me2 L and Et2 L copper halide complexes show S1 →S0 fluorescence on the ns time scale, in agreement with theory, as well as a long-lived emission. Monomeric (Me2 L)CuNCS is a white emitter, whereas dimeric [(Et2 L)Cu(μ-NCS)]2 shows intense yellow emission with a photoluminescence (PL) quantum yield of 49 %. The reaction of (Ad L)MCl (M=Cu or Au) with phenols ArOH (Ar=Ph, 2,6-F2 C6 H3 , 2,6-Me2 C6 H3 , 3,5-tBu2 C6 H3 , 2-tBu-5-MeC6 H3 , 2-pyridyl), thiophenol, or aromatic amines H2 NAr'' (Ar'=Ph, 3,5-(CF3 )2 C6 H3 , C6 F5 , 2-py) afforded the corresponding phenolato, thiophenolato and amido complexes. Although the emission wavelengths are only marginally affected by the ring substitution pattern, the PL intensities respond sensitively to the presence of substituents in the ortho or meta positions. In gold aryloxides, PL is controlled by steric factors, with strong luminescence in compounds with Au-O-C-C torsion angles <50°. Calculations confirm the dependence of oscillator strength on the torsion angle, as well as the inter-ligand charge transfer nature of the emission. The HOMO/LUMO energy levels were estimated based on first reduction and oxidation potentials.

Cooperative self-assembly and gelation of organogold(i) complexes via hydrogen bonding and aurophilic Au⋯Au interactions

With the synergistic combination of intermolecular Au(i)-Au(i) and hydrogen bonding interactions, a rod-coil alkynyl-gold(i)-isocyanide monomer tends to form supramolecular fibers and gels via a cooperative nucleation-elongation self-assembly mechanism, which display Ag(i) ion-triggered responsiveness.

Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment.

A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis(5-methyl-2-furyl)phosphino]-3,3'-di-tert-butylferrocene (5-r), and rac-1,1'-bis(diphenylphosphino)-3,3'-bis[(tri-iso-propylsilyl)oxy]ferrocene (6-r) were used to form dinuclear gold complexes. Coordination of tert-butylated ferrocenyl phosphines generated aurophilic interactions in the corresponding dinuclear gold complexes, contrary to gold(I) complexes reported with 1,1'-bis(diphenylphosphino)ferrocene. The structurally related tetraphosphine 1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene (11) also gave access to mononuclear, dinuclear, and the original trinuclear gold chloride aurophilic complexes in which 14e- to 16e- gold centers coexist. In such complexes, nonbonded ("through-space") 31P-31P' nuclear spin couplings were evidenced by high-resolution NMR. In these interactions nuclear spin information is transferred between the lone-pair electron of an uncoordinated phosphorus P and a phosphorus P' that is involved in a σ covalent bond Au-P'. The dinuclear aurophilic complex displayed a concerted shuttling of its [ClAu···AuCl] fragment between the four phosphorus donors of the tetraphosphine ligand. Thus, an aurophilic Au···Au bond, which is assumed to be a weak energy interaction, can be conserved within a dynamic shuttling process at high temperature involving an intramolecular coordination-decoordination process of digold(I) at phosphorus atoms.

Luminescence of Au(I)-thiolate complex affected by solvent

This work presents a study on the correlation between luminescence property of Au(I)-SR (SR: thiolate) complexes and solvent polarity. Luminescent [Au15(SR)14–16]+ complexes were synthesized in the weakly polar solvent of toluene, while the non-luminescent [Au7(SR)6]+ species were obtained by the same synthesis method in the polar solvent of ethanol. The dependence of luminescence intensity on the mixed solvent with various toluene/ethanol ratios was also explored. It is proposed that the luminescence of Au(I)-SR complexes originates from the aggregation of the bilayer supramolecular structures induced by the weakly polar solvent. This aggregation strengthens the intra and intercomplex aurophilic Au(I)···Au(I) interactions and subsequently enhances the luminescence intensity of the complexes.

Heterovalent Gold(I,III) complex ([Au{S2CN(CH2)6}2]3[AuCl2]2Cl]) n : Synthesis, structure, and 13C MAS NMR

The reaction of the freshly precipitated oxovanadium(IV) cyclo-hexamethylenedithiocarbamate complex with [AuCl4]– anions in a 2 M HCl solution is studied. The water-soluble heterovalent complex ([Au{S2CN(CH2)6}2]3[AuCl2]2Cl]) n (I) is formed due to the redox reaction. According to the X-ray diffraction data, structure I contains two species of complex cations [Au{S2CN(CH2)6}2]+ as conformers performing different structural functions: non-centrosymmetric cations and centrosymmetric cation B in a ratio of 2: 1. Cations A form centrosymmetric dimers [Au{2S2CN(CH2)6}4]2+ due to pairs of symmetrical secondary bonds Au…S. The aurophilic Au…Au and secondary Au…S interactions that occur between the complex cations and anions in crystal result in the formation of a polymer network.

Supramolecular self-organisation and conformational isomerism of a binuclear O,O′-dipropyl dithiophosphate gold(I) complex, [Au2{S2P(OC3H7)2}2]: Synthesis, 13C and 31P CP/MAS NMR spectroscopy, single-crystal X-ray diffraction study and thermal behaviour

Crystalline one-dimensional polymeric catena-poly[bis(μ2-O,O′-dipropyldithiophosphato-S,S′)digold(I)] (Au–Au) (1) was prepared and studied using 13C and 31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. To elucidate the structural function of Dtph ligands in crystalline gold(I) O,O′-dipropyl dithiophosphate, the chemical shift anisotropy parameters (δaniso and η) were calculated from spinning sideband manifolds in 31P MAS NMR spectra. A novel structure of the gold(I) compound comprises two isomeric, non-centrosymmetric binuclear molecules of [Au2{S2P(OC3H7)2}2] (isomers ‘A’ and ‘B’), whose four Dtph groups display structural inequivalence. In each isomeric binuclear molecule of 1, a pair of μ2-bridging dipropyl Dtph ligands almost symmetrically links two neighbouring gold atoms, forming an extensive eight-membered metallocycle [Au2S4P2], while the intramolecular aurophilic Au⋯Au bond additionally stabilises this central cyclic moiety. At the supramolecular level of complex 1, intermolecular aurophilic Au⋯Au bonds yield almost linear infinite polymeric chains (⋯‘A’⋯‘B’⋯‘A’⋯‘B’⋯)n. The thermal behaviour of this compound was studied by the simultaneous thermal analysis (STA) technique (a combination of TG and DSC) under an argon atmosphere.

Preparation, supramolecular self-organization and thermal behavior of polymeric complex of composition ([Au{S2CN(C3H7)2}2]3[Bi3Cl12]) n with unusual geometry of bismuth(III) complex anion

A reaction of freshly precipitated bismuth(III) N,N-dipropyldithiocarbamate (PDtc) with AuCl3 solution in 2 M HCl was studied. A heteropolynuclear gold(III)-bismuth complex of ionic type [Au{S2CN(C3H7)2}2]3[Bi3Cl12] (I) was isolated by crystallization of products of the heterogeneous reaction from acetone-chloroform (1: 1) solution. Crystal and supramolecular structure of compound I established by X-ray diffraction study includes structurally nonequivalent complex cations [Au{S2CN(C3H7)2}2]+ related to each other as conformers (hereinafter cations A, B, C, and D) in 1: 1: 2: 2 ratio. Due to secondary Au⋯S bonds (3.386–3.617 A), the isomeric cations form trinuclear species of two types: [C⋯A⋯C] and [D⋯B⋯D] that differ in the character of intercationic binding and Au-Au distances. Relatively weak aurophilic Au⋯Au bonds (3.4704(3) A) unite the neighboring cationic triads into zigzag polymeric chains of type (⋯[C⋯A⋯C]⋯[D⋯B⋯D]⋯)n oriented along the crystallographic axis b. The spatial isolation of neighboring chains is provided by discrete trinuclear anions [Bi3Cl12]3− where metal atoms bind four bridging (μ2 and μ3) chlorine atoms, while each bismuth atom forms distorted octahedral chromophore [BiCl6]. The complex tribismuth anion in the structure I is the first example of [Bi3Cl12]3− anion of angle rather than linear structure: Bi(1)Bi(2)Bi(3) angle is 72.358°. The thermal behavior of compound I was studied by simultaneous thermal analysis. The multistage process of thermal destruction includes the thermolysis of dithiocarbamate portion of the complex and [Bi3Cl12]3− accompanied by reduction of gold(III) to metal and release of BiCl3 (followed by its evaporation) and partial formation of Bi2S3. In the temperature range 680–760°C, bismuth sulfide undergoes oxidation to (BiO)2SO4, which decomposes above 760°C to give Bi2O3. Residue after thermolysis of compound I is gold metal and bismuth(III) oxide.

Gilded Chalices: Tetra-aurated Calix[4]arenes

Abstract 5,11,17,23-Tetrakis(trimethylsilylethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (1) was synthesised in two steps starting from 25,26,27,28-tetra-n-propoxycalix[4]arene, and the structure of 1 was determined by X-ray diffraction. Compound 1 was desilylated (K2CO3) to give 5,11,17,23- tetrakis(ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (2), which was tetra-aurated under basic conditions (NaOEt, THF) with a series of phosphane-gold chlorides (o-Tol3PAuCl, Ph3PAuCl, Ph2MePAuCl, PhMe2PAuCl, Me3PAuCl, Cy3PAuCl, t-Bu3PAuCl) to afford in good to excellent yields the tetra-aurated tetraethynylcalix[4]arene species 3-9 in one step [with phosphane ligands o-Tol3P (3), Ph3P (4), Ph2MeP (5), PhMe2P (6), Me3P (7), Cy3P (8), t-Bu3P (9)]. All compounds were characterised by 1H NMR and infrared spectroscopy, mass spectrometry and by elemental analyses, additionally 3, 4, 5, 8 and 9 by 13C{1H}, and 3-6, 8 and 9 by 31P{1H} NMR spectroscopy. The molecular structures of complexes 3 and 9 were determined by X-ray diffraction and show pinched-cone conformations, but neither intra- nor intermolecular attractive aurophilic Au···Au contacts. The acceptor ability of complexes 3 and 9 was investigated by complexation attempts with various phosphane-gold chlorides and xenon gas under pressure, but interactions could not be determined experimentally. The formation of a complex between xenon and gilded calix[4]arene could, however, be predicted for fluorine-substituted species and with very small phosphane ligands (PH3) on the basis of quantum-chemical calculations; the energy of formation is 9:6 kJ mol-1. The crystal structure of Ph2MePAuCl was also determined and shows Au···Au-bonded dimers.

ChemInform Abstract: The Ionic Mononuclear and Trinuclear Au(I)‐Complexes Ligated by Phosphine‐Functionalized Ionic Liquids: Synthesis, Characterization, and Catalysis to Hydration of Phenylacetylene.

Abstract A series of ionic Au(I)-complexes ligated by the phosphine-functionalized ionic liquids were synthesized and characterized, which are composed of the Au(I)-complex cation and the counteranion of OTf−, AuCl4−, or PF6−, respectively. The single crystal X-ray diffraction analyses show that the Au(I)-centered vector in 1A, 1B, 2A, 3A, and 4A all possess the slightly twisted linear geometry, and in each individual the Au(I)-center is coordinated by one chlorine and one imidazolium-based phosphine. The aggregation of 1B in acetone can lead to the formation of the trinuclear Au(I)-complex of 1C due to the aurophilic Au(I)–Au(I) interaction, the electrostatic attraction, and the steric preference. When these ionic Au-complexes were employed as precatalysts for hydration of phenylacetylene in aqueous-methanol media, the reaction proceeded selectively according to Markovnikov's rule with moderate to high yields of acetophenone. The highest activities were achieved over 2A with hydrophobic PF6− as the counteranion and the trinuclear 1C under mild conditions (75 °C, 2 h), in conjunction with the additive of proton acid H2SO4. The ion-pair effect on the catalytic performance of the corresponding Au(I)-complexes, coming from the phosphine-ligated cations and the counteranions, were investigated.

Polymeric gold(I) diisobutyl dithiophosphate, [Au2{S2P(O-iso-C4H9)2}2]n: Synthesis, supramolecular self-organization (a role of aurophilic interaction), 13C and 31P MAS NMR spectroscopy, and thermal behavior

A new polymeric gold(I) diisobutyl dithiophosphate (Dtph), [Au2{S2P(O-iso-C4H9)2}2]n (I), was preparatively obtained and characterized by 13C and 31P MAS NMR spectroscopy and X-ray diffraction (CIF file CCDC no. 977818). Diagrams of the χ2 statistic were constructed from the complete 31P MAS NMR spectra and used to calculate the 31P chemical shift anisotropy (δaniso = δzz − δiso) and the asymmetry parameter η = (δyy − δxx)/(δzz − δiso). The main structural unit of complex I is the noncentrosymmetric dinuclear molecule [Au2{S2P(O-iso-C4H9)2}2], in which the gold atoms are linked by two bridging ligands Dtph. The central cyclic structural fragment of the dimer [Au2S4P2] is additionally stabilized by the intramolecular aurophilic interaction Au⋯Au. Further supramolecular self-organization of the complex involves intermolecular aurophilic bonds Au⋯Au that serve to unite adjacent dinuclear molecules [Au2{S2P(O-iso-C4H9)2}2] with different spatial orientations into the polymer chains ([Au2{S2P(O-iso-C4H9)2}2])n. The thermal behavior of complex I was examined by synchronous thermal analysis under argon. The character of the thermolysis of the complex to reduced metallic gold as a final product was determined.

The ionic mononuclear and trinuclear Au(I)-complexes ligated by phosphine-functionalized ionic liquids: Synthesis, characterization, and catalysis to hydration of phenylacetylene

A series of ionic Au(I)-complexes ligated by the phosphine-functionalized ionic liquids were synthesized and characterized, which are composed of the Au(I)-complex cation and the counteranion of OTf−, AuCl4−, or PF6−, respectively. The single crystal X-ray diffraction analyses show that the Au(I)-centered vector in 1A, 1B, 2A, 3A, and 4A all possess the slightly twisted linear geometry, and in each individual the Au(I)-center is coordinated by one chlorine and one imidazolium-based phosphine. The aggregation of 1B in acetone can lead to the formation of the trinuclear Au(I)-complex of 1C due to the aurophilic Au(I)–Au(I) interaction, the electrostatic attraction, and the steric preference. When these ionic Au-complexes were employed as precatalysts for hydration of phenylacetylene in aqueous-methanol media, the reaction proceeded selectively according to Markovnikov's rule with moderate to high yields of acetophenone. The highest activities were achieved over 2A with hydrophobic PF6− as the counteranion and the trinuclear 1C under mild conditions (75 °C, 2 h), in conjunction with the additive of proton acid H2SO4. The ion-pair effect on the catalytic performance of the corresponding Au(I)-complexes, coming from the phosphine-ligated cations and the counteranions, were investigated.

Role of C–H···Au and Aurophilic Supramolecular Interactions in Gold–Thione Complexes

The role of noncovalent gold–hydrogen and aurophilic interactions in the formation of extended molecular systems of gold complexes was studied. Three new gold compounds with a heterocyclic thione ligand N-methylbenzothiazole-2-thione (mbtt), namely, [AuCl(mbtt)] (1), [AuBr(mbtt)] (2), and [Au(mbtt)2][AuI2]1–n[I3]n (3), were synthesized and characterized. The halide ligand had a considerable effect on the complex structures and thus to noncovalent contacts. Intermolecular C–H···Au and aurophilic Au···Au contacts were the dominant noncovalent interactions in structures 1–3 determining the supramolecular arrays of the gold complexes. In 1 and 2, unusual intermolecular C–H···Au gold–hydrogen contacts linked the adjacent mononuclear molecules to a chain structure, while in 3 the change in the ligand coordination induced the formation of an intermolecular aurophilic interaction. Au···I, π–π, halogen–halogen, and hydrogen bonding interactions supported further the supramolecular array of 3. The interactions were...

ChemInform Abstract: Fluoro‐, Fluoroalkyl‐, and Heterofluorogold Complexes

AbstractReview: 143 refs.

Synthesis, Structure, and Luminescent Behavior of Anionic Oligomeric and Polymeric Ag2Au2 Clusters

Mixtures of silver salts AgX (X = NO3, CF3CO2, CF3SO3) with M[Au(C6F5)2] (M = NBu4, PPh4) gave respectively the ionic mixed-metal clusters [M2{(C6F5)4Au2Ag2X2}]n (1, X = NO3; a, M = NBu4; b, M = PPh4) and [M{(C6F5)4Au2Ag2X}]n, (2a,b, X = CF3CO2; 3a,b, X = CF3SO3). The degree of aggregation n of these cluster compounds depends strongly on the method of isolation (solvent evaporation or precipitation); for example, recrystallization of 1a gave a crystalline salt of the tetraanion [(C6F5)4Au2Ag2X2]24– as well as the polymer [(NBu4)2{(C6F5)4Au2Ag2(NO3)2}]n. The aurophilic Au···Au interactions strongly influence the photoemission wavelength. The anion X has remarkably little effect on the luminescence color but strongly influences the conformation of the polyanionic chains, leading to a variety of solid-state structures, from well-defined dimers (1a1) to linear (1b) and curved (1a2, 2a) polymeric chain aggregates.