Photoluminescence studies of lanthanide ion complexes of gold and silver dicyanides: a new low-dimensional solid state class for nonradiative excited-state energy transfer

Abstract

The excited-state properties of the layered compounds M[Au(CN)2]3 and M[Ag(CN)2]3 (with M = Eu3+) have been examined. Exclusive excitation of the host ions Au(CN)2-and Ag(CN)2-leads to photoluminescence (PL) from the Eu3+ ion, indicating host to guest excited-state energy transfer. The donor Au(CN)2-and Ag(CN)2-emissions are totally quenched at all temperatures. The emission intensity from Eu[Ag(CN)2]3, [EuAg], increases with a temperature increase while the intensity for Eu[Au(CN)2]3, [EuAu], decreases. High-resolution PL data obtained at 78 K indicate that the Eu3+ ion occupies a single site in [EuAg], while multiple-site occupations are indicated in [EuAu] . The covalent Au-Au and Ag-Ag interactions in the two compounds are analyzed by comparing the splittings in the 5Do -'Fl transitions of Eu3+ as well as the intensity ratios of the electric dipole (5Do -7F2) and the magnetic dipole (5Do -7FI) transitions.

Hydrothermal synthesis, structural, Raman, and luminescence studies of Am[M(CN)2]3·3H2O and Nd[M(CN)2]3·3H2O (M=Ag, Au): Bimetallic coordination polymers containing both trans-plutonium and transition metal elements

“…The association usually extends to yield larger oligomers and one-or two-dimensional polymers. In general terms, ''aurophilic'' bonding of this type is now widely accepted as the most prominent example of a general phenomenon of metallophilicity, and is recognized as a major factor in determining supramolecular structures and properties [16][17][18]. Hence, the chemistry of Au(I) is satiated with systems that are polymeric by virtue of these Au-Au interactions.…”

“…Hence, the chemistry of Au(I) is satiated with systems that are polymeric by virtue of these Au-Au interactions. In this regard, the linear building block dicyanoaurate, [Au(CN) 2 ] À , is a convenient unit with which to explore the use of aurophilicity as a supramolecular design element [16][17][18][19][20]. This simple anion has been extensively studied over the years due it its ability to form coordination polymers through cyanide bridging.…”

Tunable excited state energy transfer in [

“…7 F 2 electric dipole transition. This is typical in crystals of this type and we propose that this indicates that the Eu 3þ ion has a high site symmetry [2].…”

“…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.…”

Dicyanometallate, VII [1] Darstellung und Kristallstruktur von Gadolinium-tris-dicyanoaurat (I), Gd[Au(CN)2]3·2,3H2O / Dicyano Metallates, VII [1] Preparation and Crystal Structure of Gadolinium-tris-dicyanoaurate (I), Gd[Au(CN)2]3·2,3H2O

“…Abschließend sei angemerkt, daß Assefa et al [14] kürzlich über eine Eu-Verbindung der Zusammensetzung Eu[Au(CN>,]3-2H-,0 berichte ten, die vermutlich isostrukurell mit der hier be schriebenen Gd-Verbindung ist. Zwar wurden bis her noch keine strukturellen Einzelheiten publiziert, doch deuten die Gitterkonstanten (a = 6,643 Ä. c = 9,138 A) auf große Ähnlichkeiten mit der von uns synthetisierten Eu-Verbindung hin (Tab.IV.).…”