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Three Novel End‐to‐End Single Azido‐Bridged Ferromagnetic Copper(II) Chains: Synthesis, Crystal Structure, and Magnetic Behavior
Author(s) -
Mukherjee Partha Sarathi,
Maji Tapas Kumar,
Escuer Albert,
Vicente Ramon,
Ribas Joan,
Rosair Georgina,
Mautner Franz A.,
Chaudhuri Nirmalendu Ray
Publication year - 2002
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 - 10.1002/1099-0682(200203)2002:4<943::aid-ejic943>3.0.co;2-m
Subject(s) - orthorhombic crystal system , chemistry , crystallography , copper , crystal structure , single crystal , magnetic susceptibility , square pyramidal molecular geometry , stereochemistry , organic chemistry
Three new single end‐to‐end azido‐bridged copper(II) chains [Cu(L1)(N 3 )] n (ClO 4 ) n ( 1 ), [Cu(L2)(N 3 )] n (ClO 4 ) n ( 2 ), and [Cu(L3)(N 3 )] n (ClO 4 ) n ( 3 ) using three different tridentate Schiff bases L1, L2, and L3, obtained from condensation of pyridine‐2‐carbaldehyde with N , N ‐dimethylethane‐1,2‐diamine, N , N ‐diethylethane‐1,2‐diamine, and 4‐(2‐aminoethyl)morpholine, respectively, have been synthesized, and their crystal structures have been determined by X‐ray diffraction methods. Complex 1 , C 10 H 15 CuN 6 ClO 4 , crystallizes in an orthorhombic system, space group P 2 1 2 1 2 1 , with a = 7.434(3), b = 12.047(4), c = 17.404(6) Å, and Z = 4; complex 2 , C 12 H 19 CuN 6 ClO 4 , crystallizes in an orthorhombic system, space group P na2 1 , with a = 14.723(5), b = 13.829(5), c = 8.002(5) Å, and Z = 4 and complex 3 , C 12 H 17 CuN 6 ClO 5 , crystallizes in an orthorhombic system, space group Pna 2 1 , with a = 13.837(15), b = 14.804(2), c = 8.050(4) Å, and Z = 4. Each structure consists of a single end‐to‐end azido‐bridged copper(II) 1D chain where each copper(II) center possesses a square pyramidal geometry. Magnetic susceptibility data, measured from 4 to 300 K, show weak ferromagnetic interaction through the end‐to‐end bridging azido pathway in all the complexes. The magnetic data were fitted to a high temperature series‐expansion for a one‐dimensional system with S = 1 / 2 local spin based on the Hamiltonian H = − J Σ S i · S i+1 for all the complexes , giving the parameters J = +2.15 cm −1 , g = 2.23 for 1 , J = +3.61 cm −1 , g = 2.16 for 2 , and J = +2.06 cm −1 , g = 2.17 for 3 . This unusual magnetic behavior through the end‐to‐end bridging azido pathway has been correlated to the structural parameters. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)