A highly luminescent tetranuclear copper(I) cluster: structure and photophysical properties

Alkynyl triphosphine copper complexes: synthesis and photophysical studies

“…The Cu-C(terminal alkyne) contacts are in the range of 1.921-1.927 Å and are expectedly shorter than the bond lengths in oligomeric copper alkynyl complexes, which typically demonstrate μ2-or μ3-bridging coordination mode of -C≡CR ligands. 37 Due to a pronounced tendency of the alkynyl ligands to bind two or more Cu(I) centers through σ−π coordination mode a significant number of tri-and tetranuclear species has been described 37, 38 but surprisingly no monomeric alkynyl complexes were characterized up to date. In this context it is worth mentioning a congener alkynyl-phosphine compound bearing an aliphatic tripod ligand, that initially thought to be monomeric, 30 which was later described as a dimer {Cu(μ2-C≡CPh)(triphos)}2 (triphos = (PPh2CH2)3CMe), 35 with only two P atoms involved in binding to the metal ion.…”

Alkynyl Coinage Metal Clusters and Complexes–Syntheses, Structures, and Strategies

“…[59] An identical structural motif is known for ap olyether-tethered bisphosphine ligand [Cu 4 ((C CPh)) 4 {(Ph 2 PCH 2 (CH 2 OCH 2 ) 2 CH 2 PPh 2 } 2 ]( 8)( Figure 5). [60] Au nique alkynylt etranuclear copperc omplex [Cu 4 (m-Ph 2 Ppypz) 4 (m 4 -h 1 h 2 -CC)](ClO 4 ) 2 (Ph 2 Ppypz = 2-(diphenylphosphino-6-pyrazol-1-yl)pyridine) (9)w as reported by Mak and co-workers. X-ray structure analysis of 9 reveals four coppera toms, which are arranged in ab utterfly shaped clusterc ore (Cu 4 C 2 )a nd bridged with two 2-(diphenylphosphino-6-pyrazol-1-yl)pyridinel igands.…”

“…[118] Despite the facile formation of the decanuclear clusters, they show interesting dynamic behaviour in solution. In af ollowing study,K oshevoy et al reported formation of hexanuclear (60). [119] These complexes consist of six gold atoms and four alkynyl ligandsc oordinated in m 2 -h 1 h 2 type, furtherb ridged by two (flexible) diphoshine ligands.…”

Observation of Non‐FCC Copper in Alkynyl‐Protected Cu53Nanoclusters

“…When dppp was then introduced, the color change was subtle.T he UV/Vis,h owever,d eveloped an additional absorption at 230 nm, which may associate with Cu I !phosphine charge transfer, in line with Cu(NO 3 ) 2 + dppp spectrum. [41] Ther esults suggest Cu II successively bonded with BP and dppp.After the formation of Cu 53 ,two characteristic absorptions were still observable but much less prominent. It might indicate asignificant portion of Cu no longer bonded with these ligands after reduction by NaBH 4 (see below).…”

“…Thed isappearance of the stretching mode of n(CÀH) at 3272 cm À1 in the FTIR of Cu(NO 3 ) 2 + BP sample indicated the bonding of BP with Cu 2+ (Supporting Information, Figure S17). [41] It gave rise to an absorption peak at 273 nm in the UV/Vis spectrum ( Figure 4A). When dppp was then introduced, the color change was subtle.T he UV/Vis,h owever,d eveloped an additional absorption at 230 nm, which may associate with Cu I !phosphine charge transfer, in line with Cu(NO 3 ) 2 + dppp spectrum.…”