An interplay between the spin density distribution and magnetic superexchange interactions: a case study of mononuclear [(n)Bu4N]2[Cu(opooMe)] and novel asymmetric trinuclear [Cu3(opooMe)(pmdta)2](NO3)2·3MeCN.
Treatment of the diethyl ester of o-phenylenebis(oxamic acid) (opbaH(2)Et(2), 1) with 5/6 equivalent of MeNH(2) in abs. EtOH results in the exclusive formation of the ethyl ester of o-phenylene(N′-methyl oxamide)(oxamic acid) (opooH(3)EtMe, 2) in ca. 50% yield. Treatment of 2 with four equivalents of [Me(4)N]OH followed by the addition of Cu(ClO(4))(2)·6H(2)O gave [Me(4)N](2)[Cu(opooMe)]·H(2)O (3A) in ca. 80% yield. As 3A appears to be a hygroscopic solid, the related [(n)Bu(4)N](+) salts [(n)Bu(4)N](2)[M(opooMe)]·H(2)O (M = Cu (3B), Ni (4)) have been synthesized. By addition of two equivalents of [Cu(pmdta)(NO(3))(2)] to a MeCN solution of 3B the novel asymmetric trinuclear complex [Cu(3)(opooMe)(pmdta)(2)](NO(3))(2) (5) could be obtained in ca. 90% yield. Compounds 2, 3A, 3B, 4 and 5 have been characterized by elemental analysis and NMR/IR spectroscopy. Furthermore, the solid state structures of 3A in the form of [Me(4)N](2)[Cu(opooMe)]·MeOH (3A′), 3B in the form of [(n)Bu(4)N](2)[Cu(opooMe)] (3B′), 4 in the form of [(n)Bu(4)N](2)[Ni(opooMe)]·1.25H(2)O (4′) and 5 in the form of [Cu(3)(opooMe)(pmdta)(2)] (NO(3))(2)·3MeCN (5′), respectively, have been determined by single-crystal X-ray diffraction studies. By controlled cocrystallization, diamagnetically diluted 3B (1%) in the host lattice of 4 (99%) in the form of single crystals have been made available, allowing single crystal EPR studies to extract all components of the g-factor and the tensors of onsite (Cu)A and transferred (N)A hyperfine interaction. Out of these studies the spin density distribution of the [Cu(opooMe)](2-) complex fragment could be determined. The magnetic properties of 5 were studied by susceptibility measurements versus temperature. An intramolecular J parameter of -65 cm(-1) has been obtained, unexpectedly, as 5 should possess two different J values due to its two different spacers between the adjacent Cu(II) ions, namely an oxamate (C(2)NO(3)) and an oxamidate (C(2)N(2)O(2)) fragment. This unexpected result is explained by a summarizing discussion of the experimentally obtained EPR results (spin density distribution) of 3B, the geometries of the terminal [Cu(pmdta)](2+) fragments of 5 determined by X-ray crystallographic studies and accompanying quantum chemical calculations of the spin density distribution of the mononuclear [Cu(opooMe)](2-) and of the magnetic exchange interactions of trinuclear [Cu(3)(opooMe)(pmdta)(2)](2+) complex fragments.
Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Strasse der Nationen 62, D-09111 Chemnitz, Germany.
Mohammad A
MA
Abdulmalic
Azar
A
Aliabadi
Andreas
A
Petr
Yulia
Y
Krupskaya
Vladislav
V
Kataev
Bernd
B
Büchner
Torsten
T
Hahn
Jens
J
Kortus
Tobias
T
Rüffer