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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A new strategy for inducing dipole moments in charge-transfer complexes: introduction of asymmetry into axially ligated iron phthalocyanines
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A new strategy for inducing dipole moments in charge-transfer complexes: introduction of asymmetry into axially ligated iron phthalocyanines

机译：一种诱导电荷转移复合物中偶极矩的新策略：不对称引入轴向连接的铁酞菁

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摘要

Introduction of asymmetry into charge-transfer complexes composed of axially ligated iron phthalocyanines was achieved. In the obtained crystals of TPP[Fe-III(Pc)(CN) Cl](2), TPP[FeIII(Pc)(CN) Br](2), and TPP [Fe-III(Pc) BrCl](2) (TPP = tetraphenylphosphonium and Pc = phthalocyanine), the axial positions of the iron atoms were occupied by 50/50 ratios of the ligands CN/Cl, CN/Br, and Br/Cl, respectively. The crystal structures of the obtained CT complexes were isostructural to those composed of the symmetric analogues of the type [Fe-III(Pc) L-2] (L = CN, Cl or Br); the [FeIII(Pc) LL'] units formed regular one-dimensional chains along the c-axis following the symmetry of the P4(2)/n space group. Despite forming similar regular chains to the symmetric systems, the electrical resistivities and activation energies were enhanced in the obtained CT complexes compared to those in symmetric systems, indicating that the charge-ordered states were stabilised by the introduction of asymmetry. More specifically, the dielectric relaxation behaviour of the inhomogeneous disordered TPP[FeIII(Pc)(CN) Cl](2) probably suggests that a dipole moment was induced in this material.
机译：实现了不对称的不对称性，实现了由轴向连接的铁酞菁组成的电荷转移复合物。在所得TPP [Fe-III（PC）（CN）（CN）（2）的晶体中，TPP [FeIII（PC）（CN）Br]（2）和TPP [Fe-III（PC）BRC1]（2 ）（TPP =四苯基膦酸铵和PC =酞菁），铁原子的轴向位置分别由50/50比的配体CN / Cl，CN / Br和Br / Cl占据。所得CT络合物的晶体结构是由[Fe-III（PC）L-2]（L = CN，CL或Br）的对称类似物组成的那些。在P4（2）/ N空间组的对称之后，[FEIII（PC）LL']沿C轴形成常规一维链。尽管与对称系统形成了类似的常规链，但与对称系统中的那些相比，在获得的CT复合物中，在所获得的CT复合物中提高了电阻率和活化能量，表明通过引入不对称来稳定电荷有序状态。更具体地，非均匀无序TPP [FeIII（PC）（CN）（CN）（2）的介电弛豫行为可能表明在该材料中诱导偶极力矩。

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