Synthesis, structure and luminescence studies of heterometallic gold(i)-copper(i) and -silver(i) alkynyl clusters/aggregates

Abstract

A series of pentanuclear gold(I)-copper(I) and -silver(I) mixed-metal alkynyl complexes, [(n)Bu(4)N][Au(3)M(2)(C triple bond CC(6)H(4)R-p)(6)] [M = Cu, R = OMe, O(n)Bu, O(n)Hex, Me, Et; M = Ag, R = Et, O(n)Hex] have been synthesized. The complexes were found to be emissive both in the solid state and in fluid solutions. DFT calculations at the B3LYP level of theory were performed on [Au(3)M(2)(C triple bond CC(6)H(4)Me-p)(6)](-) (M = Cu, Ag) to provide an understanding on the electronic structure of the complexes.

Alkynyl-functionalized gold NHC complexes and their coinage metal clusters

“…41 Also, mixed metal-metal contacts are present as shown by the moderately short Au2-Cu1 distances of 2.7920(9) Å and 2.9230(8) Å, which are much shorter than the sum of their van der Waals radii (3.06 Å) and in a similar region of comparable Au-Cu-Alkyne complexes. 20,42 Surprisingly, no coordination of any metal to the NHC-alkynyl side chains could be observed. For the reaction with the silver derivative [Ag(CCPh)] x , after three days only a single resonance in the carbene region in the 13 C{ 1 H} NMR spectrum was observed at 188.7 ppm, which can again be ascribed to a complex similar to 6.…”

Highly Luminescent Octanuclear AuI–CuI Clusters Adopting Two Structural Motifs: The Effect of Aliphatic Alkynyl Ligands

“…[9,12,13] Along the above line, we have been using a family of linear diphosphine ligands PPh 2 -spacer-PPh 2 (spacer = ÀA C H T U N G T R E N N U N G (C 6 H 4 ) n À or ÀCCÀA C H T U N G T R E N N U N G (C 6 H 4 ) m ÀCCÀ; n = 1-5, m = 0-3) to synthesize a novel class of bimetallic Au I -M I (M = Cu, Ag) intensely luminescent clusters, which belong to two main structural types depending on the nature of constituent metal ions (Scheme 1). [9,14,15] The aromatic alkynyl ligands À C C À C 6 H 4 À X employed in the synthesis of these and related complexes reported by other groups [13,16] lack to demonstrate a determinate effect on the clusters assembly process and the metal-core arrangement of the resulting products, but systematically influence their photoemission parameters via variation of the electron-donor characteristics of the X substituent. [16][17][18][19] However, the class of terminal alkynes À C C À R is not limited to Abstract: Reactions of the homoleptic (AuC 2 R) n precursors with stoichiometric amount of diphosphine ligand PPh 2 C 6 H 4 PPh 2 (P^P) and Cu + ions lead to an assembly of a new family of bimetallic clusters [Au 6 Cu 2 A C H T U N G T R E N N U N G (C 2 R) 6 …”

Early–Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity

“…[11][12][13][14] Another possibility is the synthesis of am ono-o rp olynuclear complex which can function as am etalloligand for the coordinationo fo ther metals. [6,[15][16][17][18][19][20] This approach could also be used to synthesize ELHBs of gold andz irconium and this particular combination of metals is attractive with regard to the photophysicalp roperties of the resulting complexes.G old(I) compounds often display interesting photoluminescence( PL) behaviour, [21][22][23][24][25] which can be significantly influenced by intermetallic interactions [12] in polynuclear gold compounds. [26] Zirconium complexes, in particularz irconocene-based ones,a lso often show intense PL in the visible range.…”