Search

Additional details of the thermogravimetric analysis, emissive properties, topographical steric maps, and theoretical studies (PDF)., Coordinates of the optimized structures (XYZ).

Complete experimental section; copies of 1H and 13C NMR spectra for all new compounds; copies of the absorption (UV–vis) and excitation/emission spectra of complexes 3–6; decay curves and fitting data for the determination of the half-life time of complexes 3–6; Cartesian coordinates of all new optimized complexes 3–6 in the ground state using the wB97XD and M06-2X functionals; Cartesian coordinates of S1 optimized geometries using the wB97XD and M06-2X functionals; tables of calculated orbital energies (Hartree) and metal participation, along with the HOMO–LUMO gap (eV) using the wB97XD and M06-2X functionals for the ground state of 3–6; tables with the calculated vertical transitions for the lowest T1, T2, T3, S1, and S2 excited states of 3–6 with the wB97XD and M06-2X functionals; tables with the calculated emission properties from the S1 optimized geometry for the lowest T1, T2, T3, S1, and S2 excited states of 3–6 with the wB97XD and M06-2X functionals; crystallographic tables of compounds 1a, 1e, 3c, 3d, 3g and 7h; and discussion of the structures of compounds 1a, 1e, 3c, 3d, 3g, and 7h.

In luminescent species triplet harvesting and emission through phosphorescence or thermally activated delayed fluorescence (TADF) (Figure 1) represent advantageous mechanisms which make them interesting species for OLED design. Our interest is focused on group 11 complexes displaying such properties. In this work different group 11 N-heterocyclic carbene complexes with different ancillary P, N or C ligands (L) (Figure 2) are studied. The complexes presented have been characterised by different analytical techniques: nuclear magnetic resonance (NMR), mass spectrometry and X-ray crystallography. In addition, the optical properties of the complexes, emission and excitation energies, lifetimes and quantum yields have been analysed.

Trigonal planar coordination at gold allows phosphorescent 3MC transitions, not expected for luminescent mononuclear linear gold complexes. The careful selection and nature of the ancillary ligands bonded to gold, being fluorophore groups or not emissive ligands may cause a distortion of ideal trigonal planar coordination favoring different origins for the emissions. Consequently, intraligand (IL) or charge transfer (CT) transitions may be present and besides the expected phosphorescent MC transitions, fluorescence or thermally activated delayed fluorescence (TADF) may be the origin of the luminescence. In addition of the advantages of triplet population and deactivation via phosphorescent or delayed fluorescence processes, these systems are very versatile and may show interesting properties such as mechanochromism and vapochromism and, consequently, have revealed as promising candidates for optical applications. The objective of this review is to provide an overview of the reported luminescent three-coordinated gold systems and to get insight into their emissive properties.

The goal of the work reported here was to amplify the fluorescent properties of 4-aryliden-5(4H)-oxazolones by suppression of the hula-twist non-radiative deactivation pathway. This aim was achieved by simultaneous bonding of a Pd center to the N atom of the heterocycle and the ortho carbon of the arylidene ring. Two different 4-((Z)-arylidene)-2-((E)-styryl)-5(4H)-oxazolones, the structures of which are closely related to the chromophore of the Kaede protein and substituted at the 2- and 4-positions of the arylidene ring (1a OMe; 1b F), were used as starting materials. Oxazolones 1a and 1b were reacted with Pd(OAc)2 to give the corresponding dinuclear orthometalated palladium derivates 2a and 2b by regioselective C–H activation of the ortho-position of the arylidene ring. Reaction of 2a (2b) with LiCl promoted the metathesis of the bridging carboxylate by chloride ligands to afford dinuclear 3a (3b). Mononuclear complexes containing the orthopalladated oxazolone and a variety of ancillary ligands (acetylacetonate (4a, 4b), hydroxyquinolinate (5a), aminoquinoline (6a), bipyridine (7a), phenanthroline (8a)) were prepared from 3a or 3b through metathesis of anionic ligands or substitution of neutral weakly bonded ligands. All species were fully characterized and the X-ray determination of the molecular structure of 7a was carried out. This structure has strongly distorted ligands due to intramolecular interactions. Fluorescence measurements showed an increase in the quantum yield (QY) by up to one order of magnitude on comparing the free oxazolone (QY < 1%) with the palladated oxazolone (QY = 12% for 6a). This fact shows that the coordination of the oxazolone to the palladium efficiently suppresses the hula-twist deactivation pathway.

PMMA composites and solids of complexes of formulas [AgX(P–P)]n [n = 1 and 2; X = Cl, NO3, ClO4, CF3COO, and OTf; P–P = dppb, xantphos, (PR2)2C2B10H10 (R = Ph and iPr)] display the whole palette of colors from blue to red upon selection of the anionic ligand (X) and the diphosphane (P–P). The diphosphane seems to play the most important role in tuning the emission energy and thermally activated delayed fluorescence (TADF) behavior. The PMMA composites of the complexes exhibit higher quantum yields than that of the diphosphane ligands and those with dppb are between 28 and 53%. Remarkably, instead of blue-green emissions which dominate the luminescence of silver diphosphane complexes in rigid phases, those with carborane diphosphanes are yellow-orange or orange-red emitters. Theoretical studies have been carried out for complexes with P–P = dppb, X = Cl; P–P = dppic, X = NO3; P–P = dppcc, X = Cl, NO3, and OTf and the mononuclear complexes [AgX(xantphos)] (X = Cl, Br). Optimization of the first excited triplet state was only possible for [AgX(xantphos)] (X = Cl and Br). A mixed MLCT and MC nature could be attributed to the S0 → T1 transition in these three-coordinated complexes.

Phosphorescence in the liquid crystal state with one of the highest quantum yield values, 42%, at room temperature is reported. This property is achieved with cyclic trinuclear copper(I) complexes prepared using 3,5-dimethyl-4-(trialkoxyphenyl)pyrazolate ligands. The compounds show well-organized hexagonal columnar mesophases that are stable at room temperature or near room temperature with intracolumnar order at distances of 3.6 Å, red emission and lifetimes consistent with the excimeric metal-centered phosphorescence typical of copper trinuclear pyrazolato complexes. A non-mesogenic analogue shows similar properties, and the single crystal structure is formed by stacked molecules forming a supramolecular extended structure with two different intermolecular Cu⋯Cu contacts, 3.368 Å and 3.666 Å, which are in the range of previously reported weak cuprophilic interactions. The results demonstrate that metallomesogens with efficient room temperature phosphorescence can be obtained with metal complexes other than the widely explored and precious metal-based iridium or platinum complexes.

Three cyclic trinuclear pyrazolate complexes with Au(I), Ag(I), or Cu(I) have been studied. These complexes have interesting and distinct optical and thermal properties depending on the metal, namely, liquid crystalline behavior, red or deep-red phosphorescence at room temperature, thermoluminochromism, and response to silver ions. The selected ligand, 4-hexyl-3,5-dimethylpyrazolate, maximizes the effect that the nature of the metals has on the properties of the complexes, thus allowing the intermolecular metallophilic interactions to be responsible for the optical properties. Moreover, the gold and silver complexes show columnar liquid crystal phases at high temperature. All of the complexes have good solubility properties for processing as poly(methyl methacrylate) (PMMA) doped films. Films of the gold, silver, and copper complexes show interesting optical behavior such as wide-range color switching or phosphorescence turn-on upon cooling. In addition, films of the gold complex show a bright color switching (red to blue) in the presence of silver ions. The gold and copper complexes are bright phosphors with phosphorescent quantum yields of 90% in PMMA films, the highest values reported for this class of compounds at room temperature.

Este trabajo recoge la síntesis y caracterización de complejos catiónicos y neutros de cobre(I) con el ligando 2-(2’-piridil)benzimidazol y diferentes difosfinas. Los complejos obtenidos se han empleado en la preparación de materiales compuestos con PMMA de los cuales se han estudiado sus propiedades emisoras para analizar la influencia de la variación de la difosfina y el carácter neutro o catíonico del complejo en dichas propiedades.

New complexes with the DAFO (4,5-diazafluoren-9-one) ligand of stoichiometry [Ag(DAFO)(P-P)]OTf [P-P = dppe, 1,2-bis(diphenylphosphane)ethane; dppp, 1,3-bis(diphenylphosphane)propane; dppph, ortho-bis(diphenylphosphane) benzene; dppcc, 1,2-bis(diphenylphosphane)-1,2-dicarba-closo-dodecaborane; dipcc, 1,2-bis(diisopropylphosphane)-1,2-dicarba-nido-dodecaborane], [Ag(DAFO)(P-P*)] [P-P* = dppnc, 7,8-bis(diphenylphosphane)-7,8- dicarba-nido-undecaborate(-1); dipnc, 7,8-bis(diisopropylphosphane)-7,8-dicarba- closo-undecaborate(-1)] and [Ag(DAFO)(OTf)L] [L = PPh3; dpccMe, 1-diphenylphosphane-2-methyl-1,2-dicarba-closo-dodecaborane] are reported. The structures of the complexes depend on the skeleton of the diphosphane. Most of these compounds are luminescent and their emissions seem to have originated from IL (DAFO) transitions, modified upon coordination to silver. © 2014 the Partner Organisations.

Heterobimetallic complexes of formula [M{(PPh2) 2C2B9H10}(S2C 2B10H10)M'(PPh3)] (M=Pd, Pt; M'=Au, Ag, Cu) and [Ni{(PPh2)2C2B9H 10}(S2C2B10H10) Au(PPh3)] were obtained from the reaction of [M{(PPh 2)2C2B10H10}(S 2C2B10H10)] (M=Pd, Pt) with [M'(PPh3)]+ (M'=Au, Ag, Cu) or by one-pot synthesis from [(SH)2C2B10H10], (PPh 2)2C2B10H10, NiCl 2×6 H2O, and [Au(PPh3)]+. They display d8-d10 intermetallic interactions and emit red light in the solid state at 77aK. Theoretical studies on [M{(PPh 2)2C2B9H10}(S 2C2B10H10)Au(PPh3)] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)-to->P2-M-S2> (ML') charge-transfer (LML'CT) transitions for M=Pt and to metal (M)-to->P2-M-S 2> (ML') charge-transfer (MML′CT) transitions for M=Ni, Pd. A family of red emitters of formula [M{(PPh2)2C 2B9H10}(S2C2B 10H10)M′(PPh3)] (M=Pd, Pt; M′=Au, Ag, Cu) and [Ni{(PPh2)2C2B9H 10}(S2C2B10H10) Au(PPh3)] (see figure) was synthesised. Theoretical studies on [M{(PPh2)2C2B9H10}(S 2C2B10H10)Au(PPh3)] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)-to->P2-M-S2> group (ML′) charge-transfer (LML′CT) transitions for M=Pt and to metal (M)-to->P2-M-S2> group (ML′) charge-transfer (MML′CT) transitions for M=Ni, Pd. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The metal atoms in group 11 complexes [M{(PR2)2C 2B9H10}L] [R = Ph, iPr; L = tertiary phosphane; M = Au, Ag, Cu] play an important role in the emissive properties of these compounds. The influence of the metal follows the order Au ≫ Ag ≥ Cu. The three-coordinated complexes are obtained from the reaction of [AuClL], [Ag(OTf)L], or [Cu(NO3)(PPh3)2] with the closo carborane diphosphane in refluxing ethanol. For L = PPh2NHPy, cleavage of the P-N bond and the formation of the monophosphane PPh 2OEt are observed, depending on the metal and the nido carborane diphosphane substituent (iPr or Ph). © 2013 The Royal Society of Chemistry.

[6]-Azaosmahelicenes, the first d4-heterometallahelicenes, have been synthesised and fully characterised. Their optical properties (UV-Vis absorption and luminescence) are reported.

Reaction of the diphosphanes PP [PPh2(C6H4)nPPh2 (n = 1–5) and PPh2CC(C6H4)CCPPh2] with [AuX(tht)] (X = Cl, C6F5) in a 1:2 molar ratio affords dinuclear luminescent complexes of formula [(AuX)2(PP)]. The photoemissive properties of these complexes are mainly controlled by the presence of the diphosphane ligand, specifically by the phenylene spacers of the diphosphanes. At room temperature fluorescent (IL) processes dominate the emissions, both in solution and in the solid state. Frozen solutions or solids at 77 K display dual emissions or only one emission attributed to ligand to ligand charge transfer (LL′CT) transitions from the auxiliary ligand (L) to phenylene spacers of the diphosphane (L′).

Se ha estudiado la reactividad de complejos oro y plata frente a ligandos C-dadores, fosfinas (closo o nido) y calcogenolatos derivados de carboranos, los estudios incluyen: -Complejos organometálicos [{Au(L)}2(µ-1,n-C2B10H10)] (n= 2, 7, 12), entre ellos los primeros de oro con para-carborano. A traves de calculos teóricos se compara la estabilidad de dichas especies. Se analiza el efecto de la coordinación a oro, del isómero de carborano y la monofosfina (L) en las emisiones. -Coordinación de la monofosfina [1-PPh2-2-Me-C2B10H11] y la nido-difosfina [7,8-(PPh2)2-C2B9H10]-. -Complejos de oro(III) [Au(ER)2{7,8-(PPh2)2C2B9H10}] y [Au(S-S){7,8-(PPh2)2C2B9H10}] (ER, S-S= calcogenolato) sintetizados a partir del derivado de oro(III) luminiscente [AuCl2{(PPh2)2C2B9H10}]. -El análisis de las propiedades emisoras por medio de cálculos teóricos DFT y TDDFT de [Au2{7,8-(PPh2)2C2B9H10}(C6F5)(PR3)] y [M{1,2-S2C2B10H10}{7,8-(PPh2)2C2B9H10}M'(PPh3)] con interacciones Au(I)···Au(I) o d8(M)···d10(M). -Los primeros ejemplos de complejos de oro(I) y oro(III) con ligandos [1,2-Se2-C2B10H10]2- y [1,2-Te2-C2B10H10]2-. -La síntesis de nanopartículas usando como precursores los complejos NBu4[Au(1,2-S2C2B10H10)2] y (NBu4)2[Au(7,8-S2C2B9H10)(1,2-S2C2B10H10)]

Unsaturated [TpMe2Ir(III)] fragments, readily generated from compounds [TpMe2Ir(C6H5)2(N2)], (1a) and [TpMe2Ir(¿4-CH2vC(Me)C(Me)vCH2] (1b) (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate), induce the isomerisation of the polypyridines, 2,2¿-bipyridine, 1,10-phenanthroline and 2,2¿:6¿2¿¿-terpyridine, to form complexes that contain the carbene tautomer of these ligands. For terpy, a binuclear compound has also been isolated, in which this molecule bridges two Ir(III) centres, thanks to its coordination as a bidentate N-heterocyclic carbene. The new compounds have been structurally authenticated by X-ray crystallography and their photophysical properties have been investigated.

The present study is aimed at elucidating the factors that direct the assembly of a specific family of AuI species. The assembly of AuI centers and dithiocarboxylato or xanthato ligands results in a surprising structural diversity observed by single-crystal X-ray diffraction. However, in solution, just evidences for discrete bimetallic [Au2L2] species have been observed. Interestingly, when dithiocarboxylato ligands have been used, a reversible supramolecular assembly has been observed forming the supramolecules of formulae [Au2L2]2 and [Au2L2]3. Initial studies on luminescent properties have been carried out at variable temperature. All the compounds show red emissions in the solid state at very similar energies, suggesting that the intramolecular interactions play a more relevant role in the luminescent properties than the intermolecular ones. The computational studies indicate that not only Au⋅⋅⋅Au interactions, but also Au⋅⋅⋅S and S⋅⋅⋅S ones play a role in the structure and energetic of the supramolecular species, as well as for the choice between supramolecular association or intramolecular oligomerization.

Treatment of equimolar amounts of substituted aniline or amine with substituted benzaldehyde leads to the corresponding achiral or chiral Schiff bases (L). The reaction of the bases with [Ag(O3SCF 3)(PPh3)] leads to the preparation of three or four coordinated cationic complexes, [Ag(k1-L)(PPh3) n]+ (n = 1 or 2) which have been characterized by IR, 1D and 2D NMR spectroscopy. The crystal structure of [Ag{(S)-(6-CH3)C5H3N-CHN-CH(α-CH 3)C6H5}(PPh3)2](O 3SCF3) is reported. © 2011 Elsevier B.V. All rights reserved.

A series of luminescent dinuclear neutral complexes of stoichiometry [(AuSPh)2(PPh2-(C6H4)n-PPh2)] (n = 1, 2, 3) as well as their tetranuclear cationic derivatives [(Au2SPh)2(PPh2-(C6H4)n-PPh2)2](PF6)2 are reported. Their crystal structures have been elucidated by X-ray studies. These studies indicate that, for the dinuclear species, only when n = 1 the molecules exhibit intermolecular aurophilic interactions. None of the tetranuclear species crystallizes in their molecular form, due to the formation of aggregates through Au***Au interactions. The origin of the luminescence has been analyzed by computational studies indicating that the presence or absence of aurophilic interactions does not affect the luminescent behavior and that intraligand charge transfer processes which involve the thiolate and the diphosphine are responsible for the emissions. The result is in contrast with the thiolate–gold charge transfer processes which dominate the photophysics of gold-thiolate compounds and reveals the influence of the phenylene spacers in the emissive behavior of these compounds.

A mixture of pyridoxalrhodanine, triethylphosphinegold(I) chloride, and sodium methoxide in methanol unexpectedly afforded the azacoumarin complex [Au(TS)(PEt3)] [HTS = 5-(hydroxymethyl)-8-methyl-3-thiol-7-azacoumarin], which was characterized by X-ray diffractometry. Its crystals consist of independent molecules in which the metal atom is bound to the azacoumarin [Au−S = 2.9458(18) Å] and the phosphine [Au−P = 2.262(2) Å] in an almost linear arrangement [P1−Au1−S1 = 176.93(7)°]. The complex showed better in vitro antitumor activity than cisplatin against the cisplatin-resistant cell line A2780cis.

The reaction of (SePPh2)2CH2 with group 11 metal complexes such as [Au(C6F5)3(tht)] (tht = tetrahydrothiophene) affords the complex [Au(C6F5)3(SePPh2CH2PPh2Se)] in which the ligand coordinates to the gold(III) center only through one selenium atom. The treatment of the ligand with Ag(OTf) or [Cu(NCMe)4]PF6 leads, depending on the molar ratio, to the complexes [Ag2{(SePPh2)2CH2}2](OTf)2 or [M{(SePPh2)2CH2}2]X (M = Ag, X = OTf; M = Cu, X = PF6; OTf = CF3SO3) in which the phosphine selenide ligand coordinates as a bidentate bridging or chelating ligand through the Se,Se atoms. The reaction of (SePPh2)2CH2 with [Au(C6F5)2(acac)] (acac = acetylacetonate) occurs with deprotonation of the methylene group, and the methanide complex, [Au(C6F5)2(SePPh2CHPPh2Se)], is obtained, with a bidentate chelate Se,C coordination to the gold(III) center. The selenium atom can react further with other metal complexes such as [Au(C6F5)3(tht)] to give the dinuclear species [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}], in which the ligand coordinates in a tridentate Se,C,Se form. The crystal structure of [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}] has been established by X-ray diffraction.

The complexation properties of the ligand bis(3,5-dimethylpyrazol-1-yl)methane ( L) towards group 11 metals have been studied. The reaction in a 1 : 1 molar ratio with [Cu(NCMe)4]PF6 or Ag(OTf) complexes gives the mononuclear [CuL(NCMe)]PF6 ( 1), with crystallographic mirror symmetry, or dinuclear [Ag2(µ-L)2](OTf)2 ( 2) (OTf = trifluoromethanesulfonate) in which the ligand bridges both silver centres, an unprecedented mode of coordination for this type of ligands. Compound 2 crystallizes with two water molecules and forms a supramolecular structure through classical hydrogen bonding. The reaction in a 2 : 1 ratio affords in both cases the four-coordinated derivatives [ML2]X (M = Cu, X = PF6 ( 3); Ag, X = OTf ( 4)). The treatment of [Ag(OTf)(PPh3)] with the ligand L gives [AgL(PPh3)]OTf ( 5). The gold(I) derivative [Au2(C6F5)2(µ-L)] ( 6) has also been obtained by reaction of L with two equivalents of [Au(C6F5)(tht)]. These complexes present a luminescent behaviour at low temperature; the emissions being mainly intraligand but enhanced after coordination of the metal. Compounds 1–4 have been characterized by X-ray crystallography. DFT studies showed that, in the silver complex 2, coordination of H2O to Ag in the binuclear complex is favoured by formation of a hydrogen-bonding network, involving the triflato anion, and releasing enough energy to allow distortion of the Ag2 framework.

[EN] The reactions of [AuClL] with Ag2O, where L represents the heterofunctional ligands PPh2py and PPh2CH2CH2py, give the trigoldoxonium complexes [O(AuL)3]BF4. Treatment of these compounds with thio- or selenourea affords the triply bridging sulfide or selenide derivatives [E(AuL)3]BF4 (E=S, Se). These trinuclear species react with Ag(OTf) or [Cu(NCMe)4]PF6 to give different results, depending on the phosphine and the metal. The reactions of [E(AuPPh2py)3]BF4 with silver or copper salts give [E(AuPPh2py)3M]2+ (E=O, S, Se; M=Ag, Cu) clusters that are highly luminescent. The silver complexes consist of tetrahedral Au3Ag clusters further bonded to another unit through aurophilic interactions, whereas in the copper species two coordination isomers with different metallophilic interactions were found. The first is analogous to the silver complexes and in the second, two [S(AuPPh2py)3]+ units bridge two copper atoms through one pyridine group in each unit. The reactions of [E(AuPPh2CH2CH2py)3]BF4 with silver and copper salts give complexes with [E(AuPPh2CH2CH2py)3M]2+ stoichiometry (E=O, S, Se; M=Ag, Cu) with the metal bonded to the three nitrogen atoms in the absence of AuM interactions. The luminescence of these clusters has been studied by varying the chalcogenide, the heterofunctional ligand, and the metal., [ES] La reacción de los complejos [AuClL] con Ag2O, donde L representa un ligando heterodifuncional como PPh2py y PPh2CH2CH2py, da lugar a los derivados trinucleares de oxonio, [O(AuL)3]BF4. El tratamiento de estos compuestos con tiourea o selenourea conduce a la obtención de las especies con los átomos de azufre o selenio puente a tres centros metálicos, [E(AuL)3]BF4 (E=S, Se). Estas especies trinucleares reaccionan posteriormente con Ag(OTf) o [Cu(NCMe)4]PF6 con diferentes resultados, dependiendo del ligando fosfina y del metal. La reacción de [E(AuPPh2py)3]BF4 con compuestos de plata o cobre da lugar a los clusters [E(AuPPh2py)3M]2+ (E=O, S, Se; M=Ag, Cu) que presentan una intensa luminiscencia. La estructura para los complejos de plata consiste en dos unidades tetraédricas Au3Ag que se asocian a través de interacciones aurofílicas, mientras que para los derivados de cobre se observan dos isómeros de coordinación con diferentes interacciones metalofílicas. El primer isómero es análogo a los compuestos de plata y en el segundo dos unidades [S(AuPPh2py)3]+ actúan como ligandos puente a los átomos de cobre a través de uno de los átomos de nitrógeno de una piridina. La reacción de [E(AuPPh2CH2CH2py)3]BF4 con compuestos de plata o cobre conduce a derivados de estequiometria [E(AuPPh2CH2CH2py)3M]2+ (E=O, S, Se; M=Ag, Cu) donde el metal se coordina a los tres átomos de nitrógeno, sin que haya interacciones AuM. Se ha analizado la variación de las propiedades luminiscentes de estos sistemas al modificar diversos parámetros estructurales: el calcogenuro, el ligando heterodifuncional y el metal.

The title compound, [Ag(CF3O3S)(C10H9N3)]n, is a chain polymer in which neighbouring monomeric units are related by a glide plane. The silver centre is four-coordinate; the donor atoms are one trifluoromethanesulfonate O atom and one pyridine N atom from each of two symmetry-related dipyridylamines, and an additional and unexpected AgC contact [2.6464 (16) Å] is observed to a pyridine C atom. The chains are reinforced by one classical N-HO and two `weak' C-HO hydrogen bonds.

A new series of isostructural, brilliantly luminescent gold-silver complexes having the formula [Au3(μ3-E)Ag(PPh2py)3](BF4)2 where E = O, S, Se and Ph2Ppy = 2-diphenylphosphinopyridine has been synthesized and characterized. The structural core of these complexes is a Au3Ag metallophilically linked tetrahedron with a group-16 atom functioning as a μ3-ligand capping the three gold atoms. In the solid state, pairs of clusters are joined by two unsupported aurophilic interactions. The emission energy changes strikingly in going from O (blue) to S (yellow) and Se (orange). The luminescence from the E = O system is the first to be reported for a gold(I) oxo system. Additionally, the luminescent 4-methylpyridyl analogue with E = S has been prepared and structurally characterized. For E = S, Se, the change in emission energy with μ3-bridging atom provides a sound basis for an LMMCT assignment of the excited state while lifetime measurements support its spin-forbidden nature. Frozen glass measurements indicate the presence of a higher-energy emitting state for these systems, and for the E = O system, either LMMCT or metal-centered cluster-based emission can be proposed. Copyright © 2004 American Chemical Society.