Oxidative Fusion Reactions of meso‐(Diarylamino)porphyrins

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A meso-meso-linked diphenylamine-fused porphyrin dimer and its methoxy-substituted analogue were synthesized from a meso-meso-linked porphyrin dimer by a reaction sequence involving Ir-catalyzed β-selective borylation, iodination, meso-chlorination, and S Ar reactions with diarylamines followed by electron-transfer-mediated intramolecular double C-H/C-I coupling. While these dimers commonly display characteristic split Soret bands and small oxidation potentials, they produced different products upon oxidation with tris(4-bromophenyl)aminium hexachloroantimonate. Namely, the diphenylamine-fused porphyrin dimer was converted into a dicationic closed-shell quinonoidal dimer, while the methoxy-substituted dimer gave a meso-meso, β-β doubly linked porphyrin dimer.

Section: Resultsmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

meso–meso‐Linked Diarylamine‐Fused Porphyrin Dimers

Fukui

Yorimitsu

Osuka

2016

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“…7,8‐Dehydropurpurin is known as a unique π‐extended porphyrin featuring a dual‐electronic state derived from the 18π aromatic and 20π antiaromatic conjugation circuits . Fusion of meso–meso ‐linked 10,12‐ and 18,20‐doubly phenylene‐fused porphyrin dimer gave quadruply phenylene‐fused porphyrin tape 18 , which shows a Q‐like band at 1356 nm owing to large perturbation by the fused units …”

Section: Functionalized Porphyrin Tapesmentioning

confidence: 99%

Triply Linked Porphyrinoids

Tanaka

Osuka

2018

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Triply linked porphyrin arrays, so called porphyrin tapes, are intriguing molecules in terms of their planar structures, far red-shifted absorption bands, multi-charge storage abilities, and high conductivities. Recently, porphyrin tape variants such as porphyrin-expanded porphyrin hybrid tapes, porphyrin arch-tapes, corrole tapes, and a subporphyrin tape have been explored as novel π-conjugated materials. These new molecules exhibit electronic and structural characteristics owing to direct triple linkages. This Minireview first discusses the fundamental properties of the parent porphyrin tapes and the peripherally functionalized porphyrin tapes. Then, a focus has been placed on the syntheses, structures, and unique properties of the recently explored porphyrin tape variants.

“…[2] Owing to the rigidly held planar structures, these compounds display largely perturbed electronic properties. Reductiono f 8 with HSiCl 3 gave diphenylphosphine-fused Ni II porphyrin 9.T he embedded P=Oa nd Pm oieties serve as as trong electron-accepting and electron-donatingg roup to perturb the optical and electrochemical properties of the Ni II porphyrin.…”

mentioning

confidence: 99%

“…[2] Owing to the rigidly held planar structures, these compounds display largely perturbed electronic properties. [1] Along with this strategy,w eh ave developed nitrogen-, boron-, silicon-, and carbon radical-incorporatedp orphyrins 1-4 (see below,A r= 3,5-di-tert-butylphenyl), wheret he heteroatom is embeddedi nt he fused molecular framework directly attached at the porphyrinp eriphery.…”

mentioning

confidence: 99%

Diphenylphosphine‐Oxide‐Fused and Diphenylphosphine‐Fused Porphyrins: Synthesis, Tunable Electronic Properties, and Formation of Cofacial Dimers

Fujimoto

Kasuga

Fukui

et al. 2017

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Diphenylphosphine-oxide-fused Ni porphyrin 8 was synthesized from 3,5,7-trichloroporphyrin 5 via a reaction sequence of nucleophilic aromatic substitution with lithium diphenylphosphide, oxidation with H O , and palladium-catalyzed intramolecular cyclization. Reduction of 8 with HSiCl gave diphenylphosphine-fused Ni 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 porphyrin. Ni porphyrin 9 is diamagnetic with a low-spin Ni center in solution but becomes paramagnetic with a five-coordinated Ni center with high-spin (S=1) state in the solid state. Diphenylphosphine-oxide-fused Zn 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 CDCl has been revealed to be an entropy-driven process with a large entropy gain (ΔS =207 J K mol ).