Diphenylphosphine-Oxide-Fused and Diphenylphosphine-Fused Porphyrins: Synthesis, Tunable Electronic Properties, and Formation of Cofacial Dimers,Chemistry - A European Journal

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Diphenylphosphine-Oxide-Fused and Diphenylphosphine-Fused Porphyrins: Synthesis, Tunable Electronic Properties, and Formation of Cofacial Dimers
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2017-04-24 02:55:48 , DOI: 10.1002/chem.201700909
Keisuke Fujimoto ₁ , Yuko Kasuga ₁ , Norihito Fukui ₁ , Atsuhiro Osuka ₁

Affiliation

Diphenylphosphine-oxide-fused Ni^II porphyrin 8 was synthesized from 3,5,7-trichloroporphyrin 5 via a reaction sequence of nucleophilic aromatic substitution with lithium diphenylphosphide, oxidation with H₂O₂, and palladium-catalyzed intramolecular cyclization. Reduction of 8 with HSiCl₃ gave diphenylphosphine-fused Ni^II porphyrin 9. The embedded P=O and P moieties serve as a strong electron-accepting and electron-donating group to perturb the optical and electrochemical properties of the Ni^II porphyrin. Ni^II porphyrin 9 is diamagnetic with a low-spin Ni^II center in solution but becomes paramagnetic with a five-coordinated Ni^II center with high-spin (S=1) state in the solid state. Diphenylphosphine-oxide-fused Zn^II porphyrin 10 was also synthesized and shown to form a face-to-face dimer with mutual O-Zn bonds in the crystal and in nonpolar and moderately polar solvents. The dimerization of 10 in CDCl₃ has been revealed to be an entropy-driven process with a large entropy gain (ΔS_D=207 J K⁻¹ mol⁻¹).

中文翻译：

二苯基膦-氧化物熔合和二苯基膦-熔合卟啉：合成，可调节的电子性能，和形成界面二聚体。

由3,5,7-三氯卟啉5通过亲核芳族化合物与二苯基磷化锂的取代，H ₂ O _2的氧化和钯催化的分子内环化的反应顺序，由二苯基膦氧化物稠合的Ni ^II卟啉8合成。用HSiCl ₃还原8，得到二苯基膦融合的Ni ^II卟啉9。嵌入的P ＝ O和P部分用作强电子接受基团和电子给体基团，以扰乱Ni ^II卟啉的光学和电化学性质。Ni ^II卟啉9在溶液中具有低自旋Ni ^II中心的抗磁性，但在固态时变为具有高自旋（S = 1）状态的五配位Ni ^II中心的顺磁性。还合成了二苯基膦氧化物融合的Zn ^II卟啉10，并显示在晶体以及非极性和中等极性溶剂中形成具有相互O-Zn键的面对面二聚体。CDCl _3中的10的二聚化已被证明是具有大的熵增益（ΔS _D = 207 J K ^-1 mol ^-1）的熵驱动过程。

更新日期：2017-05-19

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