Synthesis, Properties, and Crystal Structure of a Novel Anthracene-Bridged Molybdenum−Zinc Porphyrin Dimer

The synthesis and properties of novel anthracene-bridged porphyrin dimers having an oxomolybdenum(V) porphyrin
unit, H2(DPA)[MoVO(OMe)] (1) and (DPA)[MoVO(OMe)][ZnII(MeOH)] (2), and the relevant monomer porphyrin
complexes MoVO(MPP)OMe (3) and ZnII(MPP) (4) are presented. An oxomolybdenum(V) unit was introduced into
one of the two porphyrins in DPA to give 1, which has a free-base porphyrin unit. By introducing a zinc(II) ion to
the free-base part, a mixed-metal complex of 2 was prepared and isolated. The structure of 2 was analyzed by
X-ray crystallography (2·7/6CH2Cl2, triclinic, P1̄ (no. 2), a = 15.2854(12) Å, b = 19.9640(15) Å, c = 13.6915(12)
Å, α = 90.968(3)°, β = 113.108(4)°, γ = 96.501(4)°, Z = 2, R1 = 9.9, wR2 = 19.2). The structure of 2
demonstrated that a methanol is stably coordinated to the Zn(II) ion with the aid of a hydrogen bond to the methoxo
ligand on the Mo(V) ion in the binding pocket of DPA. The electrochemical measurements of 2 suggested that the
methanol was kept in the pocket of DPA in solution even at the reduced state of the molybdenum ion.

本报告详细阐述了新型蒽桥联酞菁二聚体H2(DPA)[MoVO(OMe)]（1）及其衍生物(DPA)[MoVO(OMe)][ZnII(MeOH)]（2）的合成及其性质，同时涉及相关的单分子酞菁复合物MoVO(MPP)OMe（3）和ZnII(MPP)（4）。通过在DPA的两个酞菁单元之一引入氧化钼(V)单元，制得具有游离基酞菁单元的1。向游离基部分引入锌(II)离子，制备并分离出混合金属复合物2。采用X射线晶体学对2的结构进行了分析（2·7/6CH2Cl2，三斜晶系，P1̄（编号2），a = 15.2854(12) Å，b = 19.9640(15) Å，c = 13.6915(12) Å，α = 90.968(3)°，β = 113.108(4)°，γ = 96.501(4)°，Z = 2，R1 = 9.9，wR2 = 19.2）。2的结构研究表明，甲醇通过在DPA的结合空腔中与钼(V)离子上的甲氧基配体形成氢键，稳定地与锌(II)离子配位。对2的电化学测量表明，即使在钼离子还原状态下，甲醇仍保持在DPA的结合空腔中。