Metallophilic Interactions in Closed-Shell d¹⁰ Metal−Metal Dicyanide Bonded Luminescent Systems Eu[Ag_xAu_1-x(CN)₂]₃ and Their Tunability for Excited State Energy Transfer

Abstract

We report on the heterobimetallic system, Eu[Ag(x)Au(1-x)(CN)(2)](3) (x = 0-1) in which sensitization of europium luminescence occurs by energy transfer from [Ag(x)Au(1-x)(CN)(2)](-) donor excited states. The donor states have energies which are tunable and dependent on the Ag/Au stoichiometric ratio. These layered systems exhibit interesting properties, one of which is their emission energy tunability when excited at different excitation wavelengths. In this paper, we report on their use as donor systems with Eu(III) ions as acceptor ions in energy transfer studies. Luminescence results show that the mixed metal dicyanides with the higher silver loading have a better energy transfer efficiency than the pure Ag(CN)(2)(-) and Au(CN)(2)(-) donors. The better energy transfer efficiency is due to the greater overlap between the donor emission and acceptor excitation. Additionally, more acceptor states are available in the high silver loading mixed metal Eu(III) complexes. The results from a crystal structure determination and Raman experiments are also presented in this paper and provide information about metallophilic interactions in the closed-shell d(10) metal-metal [Ag(x)Au(1-x)(CN(2)](-) dicyanide clusters.

Luminescence and simulation of mixed metal nanoclusters of dicyanoargentate(I) and dicyanoaurate(I) in alkali halides

“…Such phenomena are related to the heterometallic and homometallic metal-metal interactions [14] in these clusters. These metal-metal interactions are observed in the pure crystal case [7][8][9], in solution [6], and in doped alkali halides [5,10,12,13]. Recently, mixed nanoclusters of Au and Ag or Pt doped in zeolites have been reported to have enhanced catalytic effects on CO oxidation reactions in comparison to catalytic systems with only Au, Ag, or Pt nanoclusters present [15][16][17][18].…”

“…One important area of nanotechnology is the study of the clusters of d 8 and d 10 metal cyanide complexes [5][6][7][8][9][10][11][12][13][14]. These clusters show applications in optical memory [11], energy transfer [6], and emission tunability.…”

Syntheses, Structures and Photophysical Properties of New Heterodinuclear Cd–Ln Coordination Complexes (Ln = Sm, Eu, Tb, Nd, Ho, Er)

“…For example, in the Re-Ln and Pt-Ln complexes based on polypyridine bridging ligands and in the cyanidebridged Ru-Ln coordination complexes, the d block sensitizes the luminescence of the f block efficiently. [17] In addition, the selection of the central metal ions from the d block is extensive, for example, Os II , Cr III , Au I , Zn II , Cu I , Ag I , and so forth, [18][19][20][21][22][23] but the reports on heterometallic Cd-Ln complexes are rare. [24,25] We selected the Cd II ion to synthesize Cd-Ln complexes.…”

Tunable excited state energy transfer in [

“…Single crystals of R½MðCNÞ 2 3 (R ¼ La, Eu, Tb; M ¼ Ag, Au) have proved to have very interesting luminescent properties, most notably tunable emission energies, and have been studied extensively for this reason [1][2][3][4][5]. Crystals of R[AgðCNÞ 2 3 have been shown to have emission energies that are tunable by changing the excitation wavelength.…”