Luminescent Binuclear Gold(I) Ring Complexes

Abstract

Cyclic digold(I) complexes, containing bridging diphosphine and diacetylide ligands and with 15-to 22-membered rings, are reported. Oligomeric complexes [C 6 H 4 (OCH 2 CtCAu) 2 ] n were prepared from AuCl(SMe 2 ) and o-, m-, or p-bis(propargyloxy)benzene and then reacted with the diphosphines Ph 2 P(CH 2 ) n PPh 2 (n ) 1-6) to give the corresponding ring complexes [C 6 H 4 (OCH 2 CtCAu) 2 {µ-Ph 2 P(CH 2 ) n PPh 2 }]. Alternatively, a two-step procedure in which the soluble isocyanide complex [p-C 6 H 4 (OCH 2 CtCAuCNtBu) 2 ] was prepared, followed by displacement of the isocyanide ligands by the diphosphine, could be used. The complexes [m-C 6 H 4 (OCH 2 CtCAu) 2 (µ-Ph 2 PCH 2 PPh 2 )], [m-C 6 H 4 (OCH 2 CtCAu) 2 {µ-Ph 2 P(CH 2 ) 5 PPh 2 }], [p-C 6 H 4 (OCH 2 CtCAu) 2 {µ-Ph 2 P(CH 2 ) 3 PPh 2 }], and [p-C 6 H 4 (OCH 2 CtCAu) 2 {µ-Ph 2 P(CH 2 ) 5 -PPh 2 }] have been characterized by X-ray structure determinations. The ring complexes are emissive at room temperature and may exhibit either red or blue shifts between solution and the solid state.

Remarkable Luminescence Behaviors and Structural Variations of Two-Coordinate Gold(I) Complexes

“…Thus, the important work of Omary and coworkers on three-coordinate gold(I) has not been discussed [75,76]. Interesting polymeric gold(I) complexes prepared by Puddephatt and coworkers have also not received their share of attention here [77][78][79]. Likewise, significant work on luminescent gold-alkynyl complexes of Yam and coworkers has not fallen into the purview of the work covered in this review [80,81].…”

The influence of counter ion and ligandmethyl substitution on the solid-state structures and photophysical properties of mercury(ii) complexes with (E)-N-(pyridin-2-ylmethylidene)arylamines

“…[37][38][39] The formation of metal···metal and aryl···aryl interactions in the solid-state can cause a red shift in the emission band compared with that in solution phase. 40,41 The solid-state structures of mercury(II) halide complexes with N-donor organic ligands (monodentate) have been thoroughly studied both by spectroscopic methods as well as by X-ray crystallography, which have demonstrated a broad variety of binding modes according to the characteristics of the ligands. [42][43][44] It is well known that mercury(II) is capable of forming various coordination modes with N,N-donor atoms when suitable ligands such as bipyridine (bpy), phenanthroline (phen) and their derivatives, e.g.…”

Photoactive building blocks for coordination complexes: Gilding 2,2′:6′,2″-terpyridine

“…Gold(I) alkynyl complexes [1,2] containing gold atoms in linear coordination environments are popular building blocks for polymeric and macrocyclic organometallic assemblies [3][4][5][6][7][8][9][10][11][12]. The luminescent properties of gold(I) species [13,14] and the ease of synthesis of gold(I) alkynyls make them attractive candidates for derivatization of other metal-binding domains such as pyridine [15][16][17][18][19], 2,2'-bipyridine (bpy) [16,20,21] and 2,2':6',2"-terpyridine (tpy) [21,22].…”