Copper(ii) self-assembled clusters of bis((pyridin-2-yl)-1, 2, 4-triazol-3-yl)alkanes. Unusual rearrangement of ligands under reaction conditions. Issue 9 (13th February 2019)

• Record Type: Journal Article
• Authors: Gusev, Alexey; Nemec, Ivan; Herchel, Radovan; Shul'gin, Victor; Ryush, Irina; Kiskin, Michail; Efimov, Nickolay; Ugolkova, Elena; Minin, Vadim; Lyssenko, Konstantin; Eremenko, Igor; Linert, Wolfgang
• Is Part Of: Dalton transactions. Volume 48:Issue 9(2019)
• Page Start: 3052
• Page End: 3060
• Publication Date: 2019-02-13
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt04816a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Structure and magnetic data of new Cu(ii ) complexes on the bispyridyltriazolylalkanes basis are described. Abstract : The reaction of two structurally related bridging ligands bis[5-(2-pyridyl)-1, 2, 4-triazole-3-yl]methane (H2 L1) and bis[5-(2-pyridyl)-1, 2, 4-triazole-3-yl]ethane (H2 L2) with copper(ii ) salts resulted in a surprising wide variety of complex structures [Cu2 (H2 L1)Cl2 ]Cl2 ·4CH3 OH (1 ), [Cu4 (L1)4 ]·4H2 O (2 ), [Cu(H2 L2)(ClO4 )2 ] (3 ) and [Cu3 (OH)Na2 (L′)6 ](ClO4 )·5H2 O·C3 H6 O (4 ), where HL′ is 3, 5-bis-(pyridin-2-yl)-1, 2, 4-triazole, which were structurally characterized by the X-ray diffraction method. Complexes1 and2 were prepared on the H2 L1 basis and have binuclear and tetranuclear structures, respectively, demonstrating strong impact of the type of counter anion on the coordination mode of the ligand. In contrast, the reaction between Cu(ClO4 )2 6H2 O and H2 L2 led to the preparation of mononuclear complex3 . The reaction of H2 L2 with Cu(ClO4 )2 under alkaline conditions led to oxidative rearrangement of the ligand and the homoleptic pentanuclear complex4 with anionic ligand L′ was prepared. Magnetic properties were studied for compounds1, 2 and4 and for all of them the antiferromagnetic interactions between the Cu atoms were confirmed and analyzed by the spin Hamiltonian formalism. Furthermore, the occurrence of the antisymmetric exchange was confirmed in4 . The magnetic data analysis was supported by the X-band EPR measurements performed for complexes1, 2 and4 .