Porphyrazines as Molecular Scaffolds: Flexible Syntheses of Novel Multimetallic Complexes

Reductive deselenation of selenodiazole-fused porphyrazines, followed by acylation of the resultant labile
porphyrazinediamines, was used to prepare macrocycles bearing two Collins ligands, two oxamido residues, or
two quinoline-2-carboxamido units. Peripheral coordination of copper(II) to the di-(quinoline-2-carboxamido)-porphyrazine gave a metal-linked face-to-face porphyrazine dimer array. Sequential derivatization of the two amino
groups in the porphyrazinediamines was used to prepare mixed peripheral ligand systems including a dimetallic
picolinamido−Schiff base porphyrazine. Such systems exhibit strong metal−metal spin coupling and are anticipated
to be of value in the synthesis of novel electronic and magnetic materials.

以硒二唑稠合卟吩嗪（selenodiazole-fused porphyrazines）的还原脱硒反应，对所得不稳定卟吩嗪二胺进行酰化，可制备带有两个柯林斯配体（Collins ligands）、两个草酰胺残基或两个喹啉-2-甲酰胺基单元的大环化合物。将铜(II)与二(喹啉-2-甲酰胺基)卟吩嗪进行外围配位，可得到金属连接的面对面卟吩嗪二聚体阵列。对卟吩嗪二胺中的两个氨基开展分步衍生化，可制备包含混合外围配体的体系，例如双金属吡啶酰胺基−席夫碱（picolinamido−Schiff base）卟吩嗪。此类体系展现出强金属间自旋耦合作用，有望在新型电子与磁性材料的合成中具备应用价值。