具有[Mn9(μ2-O)12]核心结构的超分子锰(II)和锰(II)/锰(III)网格配合物。结构、磁性、氧化还原性质及表面研究。
Supramolecular Mn(II) and Mn(II)/Mn(III) grid complexes with [Mn9(mu2-O)12] core structures. Structural, magnetic, and redox properties and surface studies.
作者信息
Zhao Liang, Xu Zhiqiang, Grove Hilde, Milway Victoria A, Dawe Louise N, Abedin Tareque S M, Thompson Laurence K, Kelly Timothy L, Harvey Rosemary G, Miller David O, Weeks Laura, Shapter Joseph G, Pope Kenneth J
机构信息
Department of Chemistry, Memorial University, St. John's, Newfoundland A1B 3X7, Canada.
出版信息
Inorg Chem. 2004 Jun 28;43(13):3812-24. doi: 10.1021/ic030319v.
A series of [3 x 3] Mn(II)(9), antiferromagnetically coupled, alkoxide-bridged, square grid complexes, derived from a group of "tritopic" dihydrazide ligands, is described. The outer ring of eight Mn(II) centers in the grids is isolated magnetically from the central Mn(II) ion, leading to an S = 0 ground state for the ring, and an S = 5/2 ground state overall in each case. Exchange in the Mn(II)(8) ring can be represented by a 1D chain exchange model. Rich electrochemistry displayed by these systems has led to the production of Mn(II)/Mn(III) mixed-oxidation-state grids by both electrochemical and chemical means. Structures are reported for Mn(9)(2poap)(6)(6).10H(2)O (1), Mn(9)(2poap)(6)Mn(NCS)(4)(H(2)O)(NCS)(8).10H(2)O (2), Mn(9)(2poapz)(6)(6).14.5H(2)O (3), Mn(9)(2popp)(6)(6).12H(2)O (4), Mn(9)(2pomp)(6)(2)Cl(2).2CH(3)OH.7H(2)O (5), and Mn(9)(Cl2poap)(6)(9).7H(2)O (6). Compound 1 crystallized in the tetragonal system, space group P4(2)/n, with a = 21.568(1) A, c = 16.275(1) A, and Z = 2. Compound 2 crystallized in the triclinic system, space group P, with a = 25.043(1) A, b = 27.413(1) A, c = 27.538(2) A, alpha = 91.586(2) degrees, beta = 113.9200(9) degrees, gamma = 111.9470(8) degrees, and Z = 2. Compound 3 crystallized in the triclinic system, space group P, with a = 18.1578(12) A, b = 18.2887(12) A, c = 26.764(2) A, alpha = 105.7880(12) degrees, beta = 101.547(2) degrees, gamma = 91.1250(11) degrees, and Z = 2. Compound 4 crystallized in the tetragonal system, space group P4(1)2(1)2, with a = 20.279(1) A, c = 54.873(6) A, and Z = 4. Compound 5 crystallized in the tetragonal system, space group I, with a = 18.2700(2) A, c = 26.753(2) A, and Z = 2. Compound 6 crystallized in the triclinic system, space group P, with a = 19.044(2) A, b = 19.457(2) A, c = 23.978(3) A, alpha = 84.518(3) degrees, beta = 81.227(3) degrees, gamma = 60.954(2) degrees, and Z = 2. Preliminary surface studies on Au(111), with a Mn(II) grid complex derived from a sulfur-derivatized ligand, indicate monolayer coverage via gold-sulfur interactions, and the potential for information storage at high-density levels.
本文描述了一系列由一组“三齿”二酰肼配体衍生而来的[3×3] Mn(II)(9)反铁磁耦合、醇盐桥连的方形网格配合物。网格中八个Mn(II)中心的外环与中心Mn(II)离子磁隔离，导致环的基态为S = 0，每种情况下整体基态为S = 5/2。Mn(II)(8)环中的交换可用一维链交换模型表示。这些体系所展示的丰富电化学性质已通过电化学和化学方法制备出Mn(II)/Mn(III)混合氧化态网格。报道了Mn(9)(2poap)(6)(6).10H(2)O (1)、Mn(9)(2poap)(6)Mn(NCS)(4)(H(2)O)(NCS)(8).10H(2)O (2)、Mn(9)(2poapz)(6)(6).14.5H(2)O (3)、Mn(9)(2popp)(6)(6).12H(2)O (4)、Mn(9)(2pomp)(6)(2)Cl(2).2CH(3)OH.7H(2)O (5)和Mn(9)(Cl2poap)(6)(9).7H(2)O (6)的结构。化合物1结晶于四方晶系，空间群P4(2)/n，a = 21.568(1) Å，c = 16.275(1) Å，Z = 2。化合物2结晶于三斜晶系，空间群P，a = 25.043(1) Å，b = 27.413(1) Å，c = 27.538(2) Å，α = 91.586(2)°，β = 113.9200(9)°，γ = 111.9470(8)°，Z = 2。化合物3结晶于三斜晶系，空间群P，a = 18.1578(12) Å，b = 18.2887(12) Å，c = 26.764(2) Å，α = 105.7880(12)°，β = 101.547(2)°，γ = 91.1250(11)°，Z = 2。化合物4结晶于四方晶系，空间群P4(1)2(1)2，a = 20.279(1) Å，c = 54.873(6) Å，Z = 4。化合物5结晶于四方晶系，空间群I，a = 18.2700(2) Å，c = 26.753(2) Å，Z = 2。化合物6结晶于三斜晶系，空间群P，a = 19.044(2) Å，b = 19.457(2) Å，c = 23.978(3) Å，α = 84.518(3)°，β = 81.227(3)°，γ = 60.954(2)°，Z = 2。对Au(111)进行的初步表面研究表明，一种由硫衍生化配体得到的Mn(II)网格配合物通过金 - 硫相互作用实现单层覆盖，并具有高密度信息存储的潜力。
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