Synthesis, structures, and magnetic properties of crystals of dinuclear copper(II) and cobalt(II) complexes with 3-(3,5-dimethylpyrazol-1-yl)-6-R-1,2,4,5-tetrazines

被引:2
作者
Cherdantseva, E. V. [2 ]
Starichenko, D. V. [3 ]
Slepukhin, P. A. [1 ]
Ishmetova, R. I. [1 ]
Shvachko, Yu. N. [3 ]
Korolev, A. V. [3 ]
Rusinov, G. L. [1 ]
Ustinov, V. V. [3 ]
Matern, A. I. [2 ]
Charushin, V. N. [1 ]
机构
[1] Russian Acad Sci, I Ya Postovskii Inst Organ Synth, Ural Branch, Ekaterinburg 620041, Russia
[2] BN Yeltsin Ural State Tech Univ, Ekaterinburg 620002, Russia
[3] Russian Acad Sci, Inst Met Phys, Ural Branch, Ekaterinburg 620041, Russia
基金
俄罗斯基础研究基金会;
关键词
dinuclear complexes; 3-(3,5-dimethylpyrazol-1-yl)-6-R-1,2,4,5-tetrazines; X-ray analysis; EPR spectroscopy; SQUID magnetometry; spin magnetism;
D O I
10.1007/s11172-010-0152-x
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Dinuclear complexes of Cu-II with 3-(3,5-dimethylpyrazol-1-yl)-6-(2-hydroxyethylami-no)-1,2,4,5-tetrazine (1) and CoII with 3-(3,5-dimethylpyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5- tetrazine (2) were synthesized and structurally characterized, and the magnetic (SQUID) and resonance (EPR) properties of van der Waals crystals based on these complexes were studied. Unusual behavior of the effective magnetic moment mu(eff)(T) is observed at T < 60 K. A nonmonotonic increase in mu eff(?) for 1 (s similar to 6 %) and a 20% reduction of mu eff(?) for 2 have a common origin and are due to the influence of spin-orbital coupling on the character of the splitting between the t2g and eg levels of the central ion. Distortions of the coordination site "switch on" a positive (1) or negative (2) contribution of the orbital magnetic moment near 6 K. Irreversible temperature behavior of mu eff(T) in the heating and cooling regimes in the vicinity of 60 K suggests that the character of structural distortions and the magnetic properties are related to ligand geometry. This factor plays a significant role in crystal engineering of magnetoactive structures with polynitrogen ligands.
引用
收藏
页码:717 / 723
页数:7
相关论文
共 12 条
[1]  
CHERDANTSEVA EV, 2008, SB DOKL MEZHD K TEKH, P410
[2]   The coordination chemistry of 1,2,4,5-tetrazines [J].
Kaim, W .
COORDINATION CHEMISTRY REVIEWS, 2002, 230 (1-2) :127-139
[3]   New manganese(II) 2d-polymer with deprotonated hydroxytetrazine bridges [J].
Kiskin, MA ;
Sidorov, AA ;
Fomina, IG ;
Rusinov, GL ;
Ishmetova, RI ;
Aleksandrov, GG ;
Shvedenkov, YG ;
Dobrokhotova, ZV ;
Novotortsev, VM ;
Chupakhin, ON ;
Eremenko, IL ;
Moiseev, II .
INORGANIC CHEMISTRY COMMUNICATIONS, 2005, 8 (06) :524-528
[4]   The Jahn-Teller effect and magnetism: transition metal compounds [J].
KUGEL, KI ;
KHOMSKII, DI .
USPEKHI FIZICHESKIKH NAUK, 1982, 136 (04) :621-664
[5]  
Latosh NI, 1999, ZH ORG KHIM+, V35, P1392
[6]   Pentanuclear pivalate Ni(II) and Co(II) clusters: modulation of molecular structures and magnetic properties [J].
Malkov, AE ;
Fomina, IG ;
Sidorov, AA ;
Aleksandrov, GG ;
Egorov, IM ;
Latosh, NI ;
Chupakhin, ON ;
Rusinov, GL ;
Rakitin, YV ;
Novotortsev, VM ;
Ikorskii, VN ;
Eremenko, IL ;
Moiseev, II .
JOURNAL OF MOLECULAR STRUCTURE, 2003, 656 (1-3) :207-224
[7]   Characterisation by EPR and other techniques of La1-xCexCoO3+δ perovskite-like catalysts for methane flameless combustion [J].
Oliva, C ;
Forni, L ;
D'Ambrosio, A ;
Navarrini, F ;
Stepanov, AD ;
Kagramanov, ZD ;
Mikhailichenko, AI .
APPLIED CATALYSIS A-GENERAL, 2001, 205 (1-2) :245-252
[8]  
Ovcharenko VI, 1999, USP KHIM+, V68, P381
[9]   An unusual dinuclear ruthenium(III) complex with a conjugated bridging ligand derived from cleavage of a 1,4-dihydro-1,2,4,5-tetrazine ring. Synthesis, structure, and UV-vis-NIR spectroelectrochemical characterization of a five-membered redox chain incorporating two mixed-valence states [J].
Patra, S ;
Miller, TA ;
Sarkar, B ;
Niemeyer, M ;
Ward, MD ;
Lahiri, GK .
INORGANIC CHEMISTRY, 2003, 42 (15) :4707-4713
[10]   Spin-state transition in LaCoO3:: Direct neutron spectroscopic evidence of excited magnetic states [J].
Podlesnyak, A. ;
Streule, S. ;
Mesot, J. ;
Medarde, M. ;
Pomjakushina, E. ;
Conder, K. ;
Tanaka, A. ;
Haverkort, M. W. ;
Khomskii, D. I. .
PHYSICAL REVIEW LETTERS, 2006, 97 (24)