Hexa‐ and Octagold Chains from Flexible Tetragold Molecular Units Supported by Linear Tetraphosphine Ligands

Abstract

Flexibler Baustein: Flexible kettenförmige Tetragold(I)‐Komplexe wurden mithilfe eines neuen Tetraphosphanliganden mit Methylenbrücken hergestellt und durch Umsetzung mit KI oder NaAuCl4 in den längeren linearen Octagold(I)‐Komplex {Au8} bzw. die cyclische Hexagold(I)‐Struktur {Au6} überführt (siehe Bild; Au magenta, Cl dunkelgrün, PF6 hellgrün, I rosa). Die Tetragoldkomplexe lumineszieren überdies bei Raumtemperatur.magnified image

The 3[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

“…[40] The absorption spectra of 1 and 5 each displays two peaks at 305-310 and 348-373 nm. The former is reminiscent of the…”

“…The dpmp [36][37][38] and dpmppm [40] ligands may not be ideal for spectroscopic studies as intraligand excited states of the phenyl substituents can interfere with the spectroscopic assignments. The dmmp ligand, on the other hand, was reported to form trinuclear Au I complexes with a Au···Au···Au angle of 1368.…”

“…In literature, the available phosphine ligands for the synthesis of tri-and tetranuclear metal complexes include dpmp/dppp, [36][37][38] dmmp, [39] and dpmppm [40] (dpmp and dppp = bis(diphenylphosphinomethyl)phenylphosphine, dmmp = bis(dimethylphosphinomethyl)methylphosphine), dpmppm = bis[(diphenylphosphinomethyl)phenylphosphino]methane). The dpmp [36][37][38] and dpmppm [40] ligands may not be ideal for spectroscopic studies as intraligand excited states of the phenyl substituents can interfere with the spectroscopic assignments.…”

Stepwise Construction of Au4Ag2Cu2 Coinage Rings Supported by Linear Tetraphosphine Ligands

“…The 31 P{ 1 H} NMR spectra of 6 and 7 in [D 6 ]DMSO showed broad multiplets around 40-25 ppm and À2 to À14 ppm, corresponding to Au I and Cu I bound P nuclei in 2:2 and 3:1 ratios, respectively (see the Supporting Information). [10] The ESI-MS spectrum (see the Supporting Information) of complex 6 in dichloromethane showed di In summary, the novel octanuclear {Au I 2 Ag I Cu I } 2 ring in 1 was constructed by using flexible linear tetraphosphine dpmppm. The cluster is the first ever molecule that contains three coinage metal ions and the structure is interestingly deformed depending on the counter anions.…”

“…In the crystal packing, two adducts of {[Au 4 Ag 2 Cu 2 Cl 4 A C H T U N G T R E N N U N G (m-dpmppm) 4 ]BF 4 } 3 + are dimerized in a face-to-face arrangement (Figure 2 a) H} NMR spectral data of the related homotetranuclear complexes. [10] The conductivity of 1 was measured in DMSO at 298 K and analyzed by using Onsager theory [12] (see the Supporting Information). 6 ) 4 (2'), which was obtained in a small amount together with 2, is determined by X-ray crystallography, [11] to consist of {Au 2 AgCu} 2 octanuclear ring bridged by four tetraphosphine ligands and weakly interacted with a PF 6 À anion (Figure 3).…”