Gómez-Saiz Patricia, Gil-García Rubén, Maestro Miguel A, Pizarro José Luis, Arriortua María Isabel, Lezama Luis, Rojo Teófilo, González-Alvarez Marta, Borrás Joaquín, García-Tojal Javier
Departamento de Química, Universidad de Burgos, Misael Bañuelos s/n, 09001 Burgos, Spain.
J Inorg Biochem. 2008 Oct;102(10):1910-20. doi: 10.1016/j.jinorgbio.2008.06.015. Epub 2008 Jul 1.
New complexes of formulae Cu(HL(2))(H(2)O)(NO(3)) (1), [{Cu(L(1))(tfa)}(2)] (2), {Cu(L(1))}(2)(pz)(2) (3) and {{Cu(L(1))}(2)(dca)}(n) (4), where HL(1)=pyridine-2-carbaldehyde thiosemicarbazone, HL(2)=pyridine-2-carbaldehyde 4N-methylthiosemicarbazone, Htfa=trifluoroacetic acid (CF(3)COOH), pz=pyrazine (C(4)H(4)N(2)) and dca=dicyanamide N(CN)(2), have been synthesized and characterized. The crystal structures of these compounds are built up of monomers (1), dinuclear entities with the metal centers bridged through the non-thiosemicarbazone coligand (2 and 3) and 1D chains of dimers (4). In all the cases, square-pyramidal copper(II) ions are present, except for the square-planar ones in 3. Magnetic measurements show antiferromagnetic couplings in 2, 3 and 4. The susceptibility data were fitted by the Bleaney-Bowers' equation for copper(II) dimers derived from H=-2JS(1)S(2) being the obtained J/k values -4.8, -4.3 and -5.1K for compounds 2-4, respectively. The magnetic susceptibility of the already known {Cu(HL(1))(tfa)}(2)(2) compound has been also measured for the first time. The J/k value is -0.3K, lower than that in 2. The nuclease activity of 3 and 4 has been analyzed.
已合成并表征了通式为Cu(HL(2))(H₂O)(NO₃) (1)、[{Cu(L(1))(tfa)}₂] (2)、{Cu(L(1))}₂(pz)₂ (3) 和 {{Cu(L(1))}₂(dca)}ₙ (4) 的新型配合物,其中HL(1)=吡啶-2-甲醛硫代半卡巴腙,HL(2)=吡啶-2-甲醛4N-甲基硫代半卡巴腙,Htfa=三氟乙酸(CF₃COOH),pz=吡嗪(C₄H₄N₂),dca=双氰胺 [N(CN)₂⁻]。这些化合物的晶体结构由单体(1)、通过非硫代半卡巴腙共配体桥连金属中心的双核实体(2和3)以及二聚体的一维链(4)组成。在所有情况下,除了3中的平面正方形铜(II)离子外,均存在四方锥铜(II)离子。磁性测量表明2、3和4中存在反铁磁耦合。通过源自H = -2JS₁S₂的铜(II)二聚体的Bleaney-Bowers方程拟合磁化率数据,化合物2 - 4的J/k值分别为-4.8、-4.3和-5.1K。还首次测量了已知化合物{Cu(HL(1))(tfa)}₂₂的磁化率。J/k值为-0.3K,低于2中的值。已分析了3和4的核酸酶活性。