Poly[triaquahexa-μ-cyanido-terbium(III)trisilver(I)]: a 4f–4dbimetallic coordination polymer

Abstract

Key indicators: single-crystal X-ray study; T = 290 K; mean (N-C) = 0.006 Å; R factor = 0.019; wR factor = 0.047; data-to-parameter ratio = 10.8.The title compound, [Ag 3 Tb(CN) 6 (H 2 O) 3 ] n , consists of hydrated Tb 3+ cations that are linked with dicyanoargentate anions into a three-dimensional network. The resultant TbN 6 O 3 coordination polyhedra have a tricapped trigonal prismatic geometry. Six N atoms from the dicyanoargentate groups form the corners of the trigonal prisms, while the O atoms of three water molecules reside in the capping positions to complete the coordination environment around terbium. Argentophilic interactions give rise to a two-dimensional network of Ag atoms. All of the atoms in the structure are located on special crystallographic positions. Only one unique atom of each type is found in the structure. The site symmetry of each is: Tb (62m), Ag (2/m), C (m), N (m), O (m2m) and H (m). inorganic compounds i162 # 2007 International Union of Crystallography

Argentophilic Interactions

“…Well investigated examples have the general formula [M{Ag(CN) 2 } 3 -(H 2 O) 3 ] with M = Eu III [88,89] and Tb III . [90] The only major difference arises from the higher coordination number of the rare-earth cations (9 for Eu, instead of 6 for Co) which is established by the addition of three water molecules. In the overall layer structure the silver atoms are again assembled in planar KagomØ nets in which each silver atom is in argentophilic contacts (e.g.…”

“…A similar connectivity pattern is found in the dicyanoargentates(I) of some rare‐earth‐metal cations. Well investigated examples have the general formula [M{Ag(CN) 2 } 3 (H 2 O) 3 ] with M=Eu III[88, 89] and Tb III 90. The only major difference arises from the higher coordination number of the rare‐earth cations (9 for Eu, instead of 6 for Co) which is established by the addition of three water molecules.…”

Argentophile Wechselwirkungen

“…Gut untersuchte Beispiele haben die allgemeine Formel [M{Ag(CN) 2 } 3 (H 2 O) 3 ] mit M = Eu III [88,89] und Tb III . [90] Der einzige große Unterschied entsteht durch die hçhere Koordinationszahl der Seltenerdmetallkationen (9 für Eu anstelle von 6 für Co), die durch die Addition von drei Wassermolekülen erreicht wird. Insgesamt sind die Silberatome wieder in planaren KagomØ-Netzen angeordnet, in denen jedes Silberatom argentophile Kontakte (z.…”

Heterobimetallic lanthanide–gold coordination polymers: structure and emissive properties of isomorphous [nBu4N]2[Ln(NO3)4Au(CN)2] 1-D chains

“…The previously reported Ln[Au(CN) 2 ] 3 •nH 2 O systems have been well studied in this regard. [11][12][13][14][15][16][17][18][19][20][21][22][23][24] Throughout the Ln[Au(CN) 2 ] 3 •nH 2 O series, various optical phenomena have been observed, including the emission resulting from the efficient energy transfer from [Au(CN) 2 ] − to Ln 3+ , which is ultimately quenched at higher temperatures via a non-radiative charge transfer mechanism in the case of Ln = Eu. In the case of Ln = Tb, the energy transfer from [Au(CN) 2 ] − is not as efficient and Tb 3+ -based emission is quenched at higher temperatures.…”