一系列烷氧基二嗪配体的铜（II）配合物：单核、双核和四核实例的结构、磁性及密度泛函理论研究
Copper(II) complexes of a series of alkoxy diazine ligands: mononuclear, dinuclear, and tetranuclear examples with structural, magnetic, and DFT studies.
作者信息
Grove Hilde, Kelly Timothy L, Thompson Laurence K, Zhao Liang, Xu Zhiqiang, Abedin Tareque S M, Miller David O, Goeta Andrés E, Wilson Claire, Howard Judith A K
机构信息
Department of Chemistry, Memorial University, St. John's, Newfoundland A1B 3X7, Canada.
出版信息
Inorg Chem. 2004 Jul 12;43(14):4278-88. doi: 10.1021/ic040036i.
Picolyl hydrazide ligands have two potentially bridging functional groups (micro-O, micro-N-N) and consequently can exist in different coordination conformers, both of which form spin-coupled polynuclear coordination complexes, with quite different magnetic properties. The complex [Cu(2)(POAP-H)Br(3)(H(2)O)] (1) involves a micro-N-N bridge (Cu-N-N-Cu 150.6 degrees ) and exhibits quite strong antiferromagnetic coupling (-2J = 246(1) cm(-)(1)). [Cu(2)(PZOAPZ-H)Br(3)(H(2)O)(2)] (2) has two Cu(II) centers bridged by an alkoxide group with a very large Cu-O-Cu angle of 141.7 degrees but unexpectedly exhibits quite weak antiferromagnetic exchange (-2J = 91.5 cm(-)(1)). This is much weaker than anticipated, despite direct overlap of the copper magnetic orbitals. Density functional calculations have been carried out on compound 2, yielding a similar singlet-triplet splitting energy. Structural details are reported for [Cu(2)(POAP-H)Br(3)(H(2)O)] (1), [Cu(2)(PZOAPZ-H)Br(3)(H(2)O)(2)] (2), [Cu(2)(PAOPF-2H)Br(2)(DMSO)(H(2)O)].H(2)O (3), Cu(4)(POMP-H))(4)(4).2H(2)O (4), and PPOCCO (5) (a picolyl hydrazide ligand with a terminal oxime group) and its mononuclear complexes [Cu(PPOCCO-H)(NO(3))] (6) and [Cu(PPOCCO-H)Cl] (7). Compound 1 (C(12)H(13)Br(3)Cu(2)N(5)O(4)) crystallizes in the monoclinic system, space group P2(1)/c, with a = 15.1465(3) A, b = 18.1848(12) A, c = 6.8557(5) A, beta = 92.751(4) degrees, and Z = 4. Compound 2 (C(10)H(13)Br(3)Cu(2)N(7)O(4)) crystallizes in the triclinic system, space group P, with a = 9.14130(1) A, b = 10.4723(1) A, c = 10.9411(1) A, alpha = 100.769(1), beta = 106.271(1) degrees, gamma = 103.447(1) degrees, and Z = 2. Compound 3 (C(23)H(22)Br(2)Cu(2)N(7)O(5.5)S) crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.406(2) A, b = 22.157(3) A, c = 10.704(2) A, beta = 106.21(1) degrees, and Z = 4. Compound 4(C(52)H(48)Cu(4)N(20)O(18)) crystallizes in the monoclinic system, space group P2(1)/n, with a = 14.4439(6) A, b = 12.8079(5) A, c = 16.4240(7) A, beta = 105.199(1) degrees, and Z = 4. Compound 5 (C(15)H(14)N(4)O(2)) crystallizes in the orthorhombic system, space group Pna2(1), with a = 7.834(3) A, b = 11.797(4) A, c = 15.281(3) A, and Z = 4. Compound 6(C(15)H(13)CuN(5)O(5)) crystallizes in the monoclinic system, space group P2(1)/c, with a = 8.2818(9) A, b = 17.886(2) A, c = 10.828(1) A, beta = 92.734(2) degrees, and Z = 4. Compound 7 (C(15)H(13)CuClN(4)O(2)) crystallizes in the orthorhombic system, space group Pna2(1), with a = 7.9487(6) A, b = 14.3336(10) A, c = 13.0014(9) A, and Z = 4. Density functional calculations on PPOCCO are examined in relation to the anti-eclipsed conformational change that occurs on coordination to copper(II).
吡啶甲酰肼配体有两个潜在的桥连官能团（μ-O、μ-N-N），因此可以以不同的配位构象存在，这两种构象都会形成自旋耦合的多核配位络合物，且具有截然不同的磁性。配合物[Cu₂(POAP-H)Br₃(H₂O)]（1）涉及一个μ-N-N桥（Cu-N-N-Cu键角为150.6°），并表现出相当强的反铁磁耦合（-2J = 246(1) cm⁻¹）。[Cu₂(PZOAPZ-H)Br₃(H₂O)₂]（2）有两个由一个醇盐基团桥连的Cu(II)中心，Cu-O-Cu键角非常大，为141.7°，但出乎意料的是表现出相当弱的反铁磁交换（-2J = 91.5 cm⁻¹）。尽管铜的磁性轨道直接重叠，但这比预期的要弱得多。已对化合物2进行了密度泛函计算，得到了类似的单重态-三重态分裂能。报告了[Cu₂(POAP-H)Br₃(H₂O)]（1）、[Cu₂(PZOAPZ-H)Br₃(H₂O)₂]（2）、[Cu₂(PAOPF-2H)Br₂(DMSO)(H₂O)].H₂O（3）、Cu₄(POMP-H))₄₄.2H₂O（4）以及PPOCCO（5）（一种带有末端肟基的吡啶甲酰肼配体）及其单核配合物[Cu(PPOCCO-H)(NO₃)]（6）和[Cu(PPOCCO-H)Cl]（7）的结构细节。化合物1（C₁₂H₁₃Br₃Cu₂N₅O₄）以单斜晶系结晶，空间群为P2(1)/c，a = 15.1465(3) Å，b = 18.1848(12) Å，c = 6.8557(5) Å，β = 92.751(4)°，Z = 4。化合物2（C₁₀H₁₃Br₃Cu₂N₇O₄）以三斜晶系结晶，空间群为P，a = 9.14130(1) Å，b = 10.4723(1) Å，c = 10.9411(1) Å，α = 100.769(1)，β = 106.271(1)°，γ = 103.447(1)°，Z = 2。化合物3（C₂₃H₂₂Br₂Cu₂N₇O₅.5S）以单斜晶系结晶，空间群为P2(1)/c，a = 12.406(2) Å，b = 22.157(3) Å，c = 10.704(2) Å，β = 106.21(1)°，Z = 4。化合物4（C₅₂H₄₈Cu₄N₂₀O₁₈）以单斜晶系结晶，空间群为P2(1)/n，a = 14.4439(6) Å，b = 12.8079(5) Å，c = 16.4240(7) Å，β = 105.199(1)°，Z = 4。化合物5（C₁₅H₁₄N₄O₂）以正交晶系结晶，空间群为Pna2(1)，a = 7.834(3) Å，b = 11.797(4) Å，c = 15.281(3) Å，Z = 4。化合物6（C₁₅H₁₃CuN₅O₅）以单斜晶系结晶，空间群为P2(1)/c，a = 8.2818(9) Å，b = 17.886(2) Å，c = 10.828(1) Å，β = 92.734(2)°，Z = 4。化合物7（C₁₅H₁₃CuClN₄O₂）以正交晶系结晶，空间群为Pna2(1)，a = 7.9487(6) Å，b = 14.3336(10) Å，c = 13.0014(9) Å，Z = 4。研究了关于PPOCCO的密度泛函计算与配位到铜(II)时发生的反重叠构象变化的关系。
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