Synthesis and properties of redox‐switchable zinc complexes of 10,15,20‐triaryl‐15‐aza‐5‐oxaporphyrin

Abstract

The synthesis, aromaticity, and optical and electrochemical properties of zinc(II) complexes of 10,15,20‐triaryl‐15‐aza‐5‐oxaporphyrin (TriAAOP) were investigated. Metal‐templated cyclization of a zinc(II) 1,19‐dichloro‐5,10,15‐triaryl‐10‐azatetrapyrrin complex with an oxygen source afforded 20π TriAAOP in the neutral form. Oxidation of 20π TriAAOP with silver (I) hexafluorophosphate generated the 19π radical cation or 18π dication depending on the content of oxidant used. The interconversion between the three oxidation states (18π, 19π, and 20π) resulted in distinct changes in the aromaticity and optical properties of the 15‐aza‐5‐oxaporphyrin π‐system. Nuclear magnetic resonance spectroscopy of 20π TriAAOP revealed its antiaromatic character, whereas that of the 18π TriAAOP dication showed its aromatic character. The combined effect of the two meso‐heteroatoms was directly reflected in the redox properties of the porphyrin ring; TriAAOP was reduced more easily and more difficult to oxidize than the zinc(II) complex of 5,10,15,20‐tetraaryl‐5,15‐diaz‐aporphyrin (TADAP). In the ultraviolet‐visible‐near–infrared spectra of the materials, the lowest‐energy electronic excitations of the 19π and 18π TriAAOP derivatives were considerably red‐shifted compared with those of the isoelectronic TADAP derivatives. Based on the results of density functional theory calculations, it was concluded that the observed differences between TriAAOP and TADAP would arise from the high electronegativity of oxygen; specific frontier orbitals of the TriAAOP π‐systems were energetically stabilized relative to those of the TADAP π‐system. The present findings corroborate that the meso‐modification of a porphyrin rings with different kinds of heteroatoms is a promising strategy to fine tune their light‐response properties that are switchable by reversible single electron transfer processes.

Recent advances in the synthesis of diazaporphyrins and their chalcogen derivatives

“…Our group reported the first examples of 5,10,20-triaryl-5-aza-15-oxaporphyrinoid (RAOP) as zinc( ii ) complexes. 74 Heating a DMF solution of a bis(dipyrrin)-zinc( ii ) complex bearing two different ligands in the presence of K 2 CO 3 at 110 °C afforded the zinc( ii ) complex of 10-aryl-1,19-dichloro-5,15-dimesityl-10-azabiladiene- ac 104 quantitatively (Scheme 57). The ring-closure reaction of 104 with 4-methoxybenzaldoxime/NaH afforded RAOP 105 in the neutral 20π-electron form.…”

Synthesis and Properties of Stable 20π Porphyrinoids

“…Matano and coworkers reported 5-aza-15-oxaporphyrin and studied the cooperative effect of two different heteroatoms in the meso-positions. [55] A mixture of 1,9-dichloro-5-mesityldipyrrin 62, 1-chloro-9-(4-methoxyphenylamino)-5-mesityldipyrrin 50 c and Zn(OAc) 2 were treated in the presence of excess triethylamine in CH 2 Cl 2 /CH 3 OH at room temperature and afforded an unsymmetrical Zn complex 63 in 56 % yield (Scheme 19). The Zn complex 63 was treated with K 2 CO 3 in N, N-dimethylformamide (DMF) at 110 °C to afford the Zn(II) complex 64 in quantitative yield.…”

Dipyrrin based metal complexes: reactivity and catalysis

“…[61][62] Starting from heteroleptic complexes, dissymmetrical 5,15-diazaporphynoids could also be obtained. [63][64] These compounds were shown to be oxidized by silver salts to produce reversibly the 19π-electron radical cation and the 18π-electron dication, 36. All these compounds are stable and can be fully characterized allowing an assessment of the effect of redox state on their photophysical properties.…”