Synthesis and Design of Novel Tetranuclear and Dinuclear Gold(I) Phosphine Acetylide Complexes. First X-ray Crystal Structures of a Tetranuclear ([Au₄(tppb)(C⋮CPh)₄]) and a Related Dinuclear ([Au₂(dppb)(C⋮CPh)₂]) Complex

Abstract

Reaction of [Au(CtCR)] ∞ with dppb and tppb in CH 2 Cl 2 afforded the corresponding luminescent Au 2 (dppb)(CtCR) 2 and Au 4 (tppb)(CtCR) 4 (dppb ) 1,4-bis(diphenylphosphino)benzene; tppb ) 1,2,4,5-tetrakis(diphenylphosphino)benzene; R ) C 6 H 13 , Ph, 4-MeO-Ph); their photophysical properties have been studied, and the X-ray crystal structures of Au 2 (dppb)(CtCPh) 2 (2) and Au 4 (tppb)(CtCPh) 4 ( 5) have been determined. Close Au‚‚‚Au contacts are present in 5, which twisted the six-membered ring that comprises the PAu 2 PC 2 unit. Such a structure is reminiscent of a distorted anthracene-like unit containing Au atoms as part of the heterocycle, owing to the auriophilicity which brings the Au atoms into close contact.

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

“…Although the general method used to synthesize related compounds involves a direct reaction between the polymer [Au(CuC-R)] n and the free phosphanes ( polymer method), 41,42,50,55 the laborious syntheses of 5-ethynyl-2,2′-bipyridine, and 4′-ethynyl-2,2′:6′,2″-terpyridine and the moderate yields of these reactions prompted us to assay an alternative strategy based on the reaction of acetylacetonato phosphane complexes with the terminal alkynes ("acac method"). 63,64 In fact, the acac derivatives (triphosphane = triphos (9) and triphosph (10)) and [Au 4 (CuC-C 15 H 10 N 3 ) 4 (μ 4 -tetraphosphane)] (tetraphos (11), tpbz (12) and dppeda (13)) were obtained by reacting [Au(CuC-C 15 H 10 N 3 )] n and the appropriate polyphosphane.…”

“…However, neither tri nor tetratopic analogous systems have been described so far. Indeed, although phosphanes and diphosphanes have been widely used as ligands in the chemistry of alkynyl gold(I) compounds, 25 the number of derivatives based on tri or tetradentate phosphanes is rather limited, 36,39,[55][56][57][58][59] despite their potential in the construction of multimetallic assemblies. The use of tri or tetratopic building blocks should increase the complexity of the obtained heterometallic frameworks, allowing the obtention of architectures with a great diversity of nuclearities and/or topologies and unique properties.…”

Design and Synthesis of Calixarene‐Based Bis‐alkynyl‐Bridged Dinuclear AuI Isonitrile Complexes as Luminescent Ion Probes by the Modulation of Au⋅⋅⋅Au Interactions

“…[10][11][12][13][14][15][16][17][18] A number of di-, tri-, and polynuclear gold(I) complexes have been reported by us [10][11][12][13][14][15] and others [16][17][18] to show strong phosphorescence, mainly in the yellowish-green to red region, with Au···Au interactions playing an important role in governing the unique electronic absorption and emission features in these complexes. In general, an increase in the Au···Au interaction would lead to a shift of the emission to lower energy.…”

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

“…[238] Einen interessanten Beitrag zur Dendrimerchemie lieferten Puddephatt et al, die trifunktionelle Kern-Moleküle wie 1,3,5-Triethinylaurylbenzol zu polymeren Verbindungen verknüpften (Schema 53). [239] Intramolekulare Au···Au-Wechselwirkungen (3.15 ) sowie starke Lumineszenz und ein langlebiger angeregter Zustand [240] wurden für eine Serie von zweikernigen und vierkernigen Au I -Alkinylkomplexen vom Typ [Au 2 (m-dppb)(CCR) 2 ] und [Au 4 (m 4 -tppb)(CCR) 4 ] beschrieben (dppb = 1,4-Bis(diphenylphosphanyl)benzol, tppb = 1,2,4,5-Tetrakis(diphenylphosphanyl)benzol;…”

“…Die Emission im Festzustand war gegenüber der in Lösung deutlich rotverschoben, vermutlich wegen der Stapelwechselwirkung zwischen den Phenylringen der Alkinylgruppen und dem Isocyanidrest der beiden unmittelbar benachbarten Moleküle. In den von Yam et al [240] beschriebenen Phosphan-verbrückten Komplexen (Schema 54 a) wird der zentrale Phenylring mit steigender Zahl an PPh 2 R-Substituenten elektronenärmer, was zu einer Rotverschiebung der Energie des Übergangs führt. Dass der Gang der Absorptionskoeffizienten ungefähr parallel zur Erhöhung der Zahl der Goldalkinyleinheiten verläuft, lässt eine Anwendung dieser Komplexe als lichtsammelnde Systeme möglich erscheinen.…”