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Copper(II) Clusters of Two Pairs of 2,3‐Dihydroxybutanedioyl Dihydrazones: Synthesis, Structure, and Magnetic Properties
Author(s) -
Chen Zilu,
Zhou Suping,
Shen Yanling,
Zou Huahong,
Liu Dongcheng,
Liang Fupei
Publication year - 2014
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.201402784
Subject(s) - chemistry , crystallography , enantiomer , salicylaldehyde , stereochemistry , copper , crystal structure , schiff base , organic chemistry
Abstract Condensation reactions of (2 R ,3 R )‐ and (2 S ,3 S )‐2,3‐dihydroxybutanedihydrazide with salicylaldehyde and 3‐methoxysalicylaldehyde gave two enantiomeric pairs, (2 R ,3 R )/(2 S ,3 S )‐2,3‐dihydroxybutanedioylbis(salicylaldehydehydrazone) [(2 R ,3 R )‐BSH and (2 S ,3 S )‐BSH] and (2 R ,3 R )/(2 S ,3 S )‐2,3‐dihydroxybutanedioyl bis(3‐methoxysalicylaldehydehydrazone) [(2 R ,3 R )‐MBSH and (2 S ,3 S )‐MBSH]. Their reactions with Cu II salts provided two chiral hexanuclear clusters [Cu 6 L 2 (C 5 H 5 N) 10 ] 2 [C 5 H 6 N] 3 (ClO 4 ) 7 · (CH 3 OH) · (C 5 H 5 N) [L = (2 R ,3 R )‐BSH; (2 S ,3 S )‐BSH] and four chiral tridecanuclear clusters [Cu 13 L 3 (OH) 2 (CH 3 COO) 6 (C 5 H 5 N) 6 (DMF) 3 ] · 6DMF · 3H 2 O [L = (2 R ,3 R )‐BSH; (2 S ,3 S )‐BSH] and [Cu 13 X 3 (OH) 2 (CH 3 COO) 6 (C 5 H 5 N) 2 (DMF) 8 ] · 6H 2 O [X = (2 R ,3 R )‐MBSH, (2 S ,3 S )‐MBSH]. Their structures were determined by single‐crystal X‐ray diffraction analysis. All six compounds are enantiomers of each other. The two hexanuclear clusters exhibit two orthogonal linear trinuclear units. The two pairs of tridecanuclear clusters display esthetic structures with different symmetries; they feature rare heptanuclear vertex‐sharing dicubane cores and their six unshared Cu II vertexes are linked to another six Cu II ions. These represent the first examples of chiral clusters bearing dicubane cores. Magnetic studies revealed the presence of overall antiferromagnetic interactions in these compounds.