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锰（III）-金属（II）配合物[Mn(MeOH)L(OH)M(bpy)]₂（M = Zn、Cu、Ni和Mn；H₄L = 1,2-双（2-羟基苯甲酰胺基）苯；bpy = 2,2'-联吡啶）的合成、磁性及不完全双立方烷结构

Synthesis, Magnetic Properties, and Incomplete Double-Cubane Structure of Manganese(III)-Metal(II) Complexes [Mn(MeOH)L(OH)M(bpy)](2) (M = Zn, Cu, Ni, and Mn; H(4)L = 1,2-Bis(2-hydroxybenzamido)benzene; bpy = 2,2'-Bipyridine).

作者信息

Sunatsuki Yukinari, Shimada Hiromitsu, Matsuo Toshihiro, Nakamura Masaaki, Kai Fumiaki, Matsumoto Naohide, Re Nazzareno

机构信息

Department of Chemistry, Faculty of Science, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan, and Dipartmento di Chimica, Universita di Perugia, via Elce di Sotto 8, 06100 Perugia, Italy.

出版信息

Inorg Chem. 1998 Oct 19;37(21):5566-5574. doi: 10.1021/ic980543y.

DOI:10.1021/ic980543y
PMID:11670703
Abstract

The manganese(III) complex K[MnL(py)(2)].py (H(4)L = 1,2-bis(2-hydroxybenzamido)benzene, py = pyridine) reacted as a ligand complex at the two phenoxo oxygen atoms with metal(II) ion and 2,2'-bipyridine to give a series of heterometal complexes Mn(MeOH)L(OH)M(bpy) (M(II) = Zn (1); Cu (2); Ni (3); Mn (4)). X-ray structures were determined 1, C(68)H(74)N(8)O(18)Mn(2)Zn(2): a = 12.367(3) Å, b = 12.844(2) Å, c = 12.262(2) Å, alpha = 106.58(1) degrees, beta = 117.89(1) degrees, gamma = 78.57(2) degrees, triclinic, P&onemacr;, and Z = 1. 2, C(68)H(74)N(8)O(18)Mn(2)Cu(2): a = 13.447(1) Å, b = 12.670(2) Å, c = 21.732(1) Å, beta = 107.076(5) degrees, monoclinic, P2(1)/n, and Z =2. 3, C(68)H(74)N(8)O(18)Mn(2)Ni(2): a = 12.358(3) Å, b = 12.847(3) Å, c = 12.315(3) Å, alpha = 106.63(2) degrees, beta = 118.71(1) degrees, gamma = 78.32(2) degrees, triclinic, P&onemacr;, and Z = 1. 4, C(66)H(66)N(8)O(16)Mn(4): a = 12.511(2) Å, b = 21.129(3) Å, c = 12.811(1) Å, beta = 110.12(1) degrees, monoclinic, P2(1)/n, and Z = 2. The X-ray analyses confirmed that each of the crystals consists of an incomplete double-cubane molecule with a [Mn(2)M(2)O(6)] core, in which two M(II) ions are bridged by two hydroxo groups to form a planar dinuclear moiety bridged by di-&mgr;-hydroxo groups (bpy)M(OH)(2)M(bpy) and the dinuclear moiety is sandwiched between two Mn(III) complexes Mn(MeOH)L. The Mn(III) ion and the dinuclear M(II) moiety are triply bridged by the one hydroxo oxygen of the dinuclear moiety and two phenoxo oxygen atoms of the Mn(III) ligand complex. The two phenoxo oxygen atoms of the Mn(III) ligand complex coordinate as an axial ligand to two independent metal(II) ions of the dinuclear moiety. The magnetic susceptibilities of 1-4 were measured in the temperature range of 2-300 K. All the Mn(III) ions in these complexes are in a high-spin state of S(Mn) = 2 with a d(4) electronic configuration, and the metal(II) ions are in the spin states of S(Zn) = 0, S(Cu) = 1/2, S(Ni) = 1, and S(Mn(II)) = 1/2 (low-spin). The magnetic susceptibility data are well reproduced by the following spin Hamiltonian based on the rhombus spin coupling model with spin (S(1), S(2), S(3), S(4)) = (2, S(M), 2, S(M)), including a zero-field splitting term for the Mn(III) centers: H = g(Mn)beta(S(1) + S(3)).H + g(M)beta(S(2) + S(4)).H - 2J(S(1).S(2) + S(2).S(3) + S(3).S(4) + S(4).S(1)) - 2J'(S(2).S(4)) + D(Mn)[S(1z)(2) + S(3z)(2)], in which g(Mn) and g(M) are the g factors of the Mn(III) and M(II) ions, J and J' are the Mn(III)-M(II) and M(II)-M(II) Heisenberg coupling constants, and D is the zero-field splitting parameter of Mn(III). The calculated best-fit parameters are as follows: g(Mn) = 1.91, g(Cu) = 2.39, J = -4.5 cm(-)(1), J' = -8.1 cm(-)(1), and D(Mn) = -4.9 cm(-)(1) for 2; g(Mn) = 1.97, g(Ni) = 2.23, J = -1.5 cm(-)(1), J' = -2.6 cm(-)(1), and D(Mn) = -5.5 cm(-)(1) for 3; and g(Mn) =1.95, g(Mn(II)) = 2.29, J = -3.5 cm(-)(1), J' = -14.1 cm(-)(1), and D(Mn) = -12.0 cm(-)(1) for 4. The spin frustration due to the incomplete double-cubane structure is discussed.

摘要

锰（III）配合物K[MnL(py)(2)].py（H(4)L = 1,2 - 双（2 - 羟基苯甲酰胺基）苯，py = 吡啶）在两个酚氧基氧原子处作为配体配合物与金属（II）离子和2,2'-联吡啶反应，得到一系列异金属配合物Mn(MeOH)L(OH)M(bpy)（M(II) = Zn (1)；Cu (2)；Ni (3)；Mn (4)）。测定了1、C(68)H(74)N(8)O(18)Mn(2)Zn(2)的X射线结构：a = 12.367(3) Å，b = 12.844(2) Å，c = 12.262(2) Å，α = 106.58(1)°，β = 117.89(1)°，γ = 78.57(2)°，三斜晶系，P&onemacr;，Z = 1。2、C(68)H(74)N(8)O(18)Mn(2)Cu(2)的结构：a = 13.447(1) Å，b = 12.670(2) Å，c = 21.732(1) Å，β = 107.076(5)°，单斜晶系，P2(1)/n，Z = 2。3、C(68)H(74)N(8)O(18)Mn(2)Ni(2)的结构：a = 12.358(3) Å，b = 12.847(3) Å，c = 12.315(3) Å，α = 106.63(2)°，β = 118.71(1)°，γ = 78.32(2)°，三斜晶系，P&onemacr;，Z = 1。4、C(66)H(66)N(8)O(16)Mn(4)的结构：a = 12.511(2) Å，b = 21.129(3) Å，c = 12.811(1) Å，β = 110.12(1)°，单斜晶系，P2(1)/n，Z = 2。X射线分析证实，每个晶体均由一个具有[Mn(2)M(2)O(6)]核心的不完全双立方烷分子组成，其中两个M(II)离子通过两个羟基桥连形成一个由双 - μ - 羟基基团(bpy)M(OH)(2)M(bpy)桥连的平面双核部分，并且该双核部分夹在两个锰（III）配合物Mn(MeOH)L之间。锰（III）离子和双核M(II)部分通过双核部分的一个羟基氧和锰（III）配体配合物的两个酚氧基氧原子三重桥连。锰（III）配体配合物的两个酚氧基氧原子作为轴向配体与双核部分的两个独立金属（II）离子配位。在2 - 300 K的温度范围内测量了1 - 4的磁化率。这些配合物中的所有锰（III）离子均处于S(Mn) = 2的高自旋态，具有d(4)电子构型，金属（II）离子处于S(Zn) = 0、S(Cu) = 1/2、S(Ni) = 1和S(Mn(II)) = 1/2（低自旋）的自旋态。基于菱形自旋耦合模型，自旋（S(1)，S(2)，S(3)，S(4)) = (2，S(M)，2，S(M))，包括锰（III）中心的零场分裂项，通过以下自旋哈密顿量很好地再现了磁化率数据：H = g(Mn)β(S(1) + S(3)).H + g(M)β(S(2) + S(4)).H - 2J(S(1).S(2) + S(2).S(3) + S(3).S(4) + S(4).S(1)) - 2J'(S(2).S(4)) + D(Mn)[S(1z)(2) + S(3z)(2)]，其中g(Mn)和g(M)是锰（III）和M(II)离子的g因子，J和J'是锰（III） - M(II)和M(II) - M(II)海森堡耦合常数，D是锰（III）的零场分裂参数。计算得到的最佳拟合参数如下：对于2，g(Mn) = 1.91，g(Cu) = 2.39，J = -4.5 cm(-)(1)，J' = -8.1 cm(-)(1)，D(Mn) = -4.9 cm(-)(1)；对于3，g(Mn) = 1.97，g(Ni) = 2.23，J = -1.5 cm(-)(1)，J' = -2.6 cm(-)(1)，D(Mn) = -5.5 cm(-)(1)；对于4，g(Mn) = 1.95，g(Mn(II)) = 2.29，J = -3.5 cm(-)(1)，J' = -14.1 cm(-)(1)，D(Mn) = -12.0 cm(-)(1)。讨论了由于不完全双立方烷结构导致的自旋阻挫。

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