In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2012, No. 34 ( 2012-12), p. 5729-5740
Abstract:
The synthesis and characterization of three monohydroxido‐bridged dinuclear Cu II complexes, [{Cu 2 (L 1 ) 2 (μ‐OH)}(ClO 4 ){Cu 2 (L 1 ) 2 (μ‐OH)}](ClO 4 ) · 5.5H 2 O ( 1 ), Cu 2 (L 2 ) 2 (OH)(ClO 4 )(H 2 O) 2 ( 2 ), [{Cu 2 (L 3 ) 2 (μ‐OH)(ClO 4 )} 2 ] · 5H 2 O ( 3 ) and three monohydroxido‐bridged trinuclear Cu II complexes, [Cu 3 (L 4 ) 3 (μ 3 ‐OMe)(ClO 4 ) 2 ] ( 4 ), [Cu 3 (L 5 ) 3 (μ 3 ‐OH) (ClO 4 ) 2 ] · 0.5{(CH 3 ) 2 CO} · 0.5(H 2 O) ( 5 ), [Cu 3 (L 6 ) 3 (μ 3 ‐OH)(ClO 4 ) 2 ] ( 6 ), is reported (HL 1 –HL 6 = tridentate N 2 O ligands resulting from the Schiff base condensation of salicylaldehyde or 3‐methoxysalicylaldehyde with ethylenediamine, 1,2‐diaminopropane, 2‐methylpropane‐1,2‐diamine or 1,2‐diaminocyclohexane). The six new complexes are obtained through aggregation of the corresponding mononuclear precursor Cu(L i )(py)(ClO 4 ) in the presence of HO – (MeO – ) anions in methanol. The nuclearity of the resulting complex depends on the steric requirement of L i : in the presence of an OMe substituent α to the O phenoxido atom (L 1 –L 3 ), μ‐HO – single‐bridged dinuclear compounds are obtained ( 1 – 3 ); in the absence of an α‐substituent (L 4 –L 6 ), the aggregation proceeds to the μ 3 ‐OH – (μ 3 ‐OMe – ) bridged trinuclear compounds 4 – 6 . The molecular structures of 1 , 3 and 4 – 6 have been established through single‐crystal X‐ray studies. Antiferromagnetic interactions operate in 1 ( J = –57 cm –1 , –2 JS 1 S 2 formalism), 2 is paramagnetic, and 3 is the first example of a ferromagnetic monohydroxido‐bridged dinuclear Cu II complex ( J = 16 cm –1 ). The structural and magnetic parameters for the 22 μ‐HO – single‐bridged dinuclear Cu II compounds reported to date are compared. Antiferromagnetic interactions operate in all three monohydroxido‐bridged trinuclear Cu II complexes 4 , 5 , and 6 ( J = –16.9, –6.3, and –6.7 cm –1 , respectively). The structural and magnetic parameters for the seven μ 3 ‐hydroxido (methoxido) bridged trinuclear Cu II compounds presently known in the series based on tridentate Schiff bases that result from condensation of diamines with salicylaldehydes are compared.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2012.34
DOI:
10.1002/ejic.201200819
Language:
English
Publisher:
Wiley
Publication Date:
2012
detail.hit.zdb_id:
1475009-0
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