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Hydrothermal Syntheses, Crystal Structures, Magnetism and Fluorescence Quenching of Oxamidato‐Bridged Pentanuclear Cu II 4 Ln III Complexes Containing Macrocyclic Ligands (Ln = Eu, Tb) and the Crystal Structure of a Hexanuclear Ni II 5 Sm III Complex
Author(s) -
Sun YaQiu,
Liang Mao,
Dong Wen,
Yang GuangMing,
Liao DaiZheng,
Jiang ZongHui,
Yan ShiPing,
Cheng Peng
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300464
Subject(s) - chemistry , oxamide , crystallography , perchlorate , crystal structure , hydrogen bond , supramolecular chemistry , molecule , square pyramid , stereochemistry , ion , organic chemistry
Three novel oxamidato‐bridged complexes incorporating a macrocyclic oxamide of formula [(CuL) 3 {CuL(C 2 H 5 OH)}Eu(H 2 O)](ClO 4 ) 3 ·1.5H 2 O ( 1 ), [(CuL) 3 {CuL(C 2 H 5 OH)}Tb(H 2 O)](ClO 4 ) 3 ·2H 2 O ( 2 ) and [(NiL) 5 Sm](ClO 4 ) 3 ·2H 2 O ( 3 ) (CuL and NiL, H 2 L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclopentadeca‐7,13‐dien), have been hydrothermally synthesized and structurally characterized. In these complexes, the central Ln III and external copper (or nickel) ions are bridged by macrocyclic oxamide groups. The Eu III (or Tb III ) ion of 1 (or 2 ) resides in a distorted tricapped trigonal prismatic environment surrounded by eight oxygen atoms from four oxamide groups and one oxygen atom from a water molecule, whereas the Sm III ion of 3 resides in a distorted bicapped square antiprismatic environment surrounded by ten oxygen atoms from five oxamide groups. Furthermore, there are hydrogen bonding interactions in 1 and 2 between perchlorate, ethanol and water moieties. Especially for 1 and 2 , O−H ··· O and weak coordination of ClO 4 − groups link the pentanuclear fragments and perchlorate ions to form a 1‐D supramolecular architecture. The fluorescence of Eu III and Tb III are almost completely quenched in 1 and 2 . The magnetic properties of 1 and 2 have been characterized. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)