An Expanded Porphycene with High NIR Absorptivity That Stabilizes Two Different Kinds of Metal Complexes

From the reaction of sterically less hindered tetrapropyl[24]dithiaamethyrin(1.0.0.1.0.0) 5, with [Rh(CO)2Cl]2, a unique anti form of the bis(dicarbonylrhodium(I)) complex (6‐anti), where two rhodium ions are on the opposite faces of the macrocyclic ligand, was isolated for the first time in 12% yield along with the corresponding syn isomer (6‐syn, 61% yield). These structures were characterized in detail by single‐crystal X‐ray structure analysis. Compound 6‐syn exhibited a bowl‐shaped structure with the two rhodium atoms separated by a distance of ∼4.5 Å. In contrast, 6‐anti contained a wave‐shaped macrocycle with a distance of ∼5.3 Å between the two rhodium atoms. Furthermore, the 1H nuclear magnetic resonance spectra and density functional theory calculation results revealed that 6‐anti had a stronger paratropic ring current and a more planar structure than 6‐syn. The isolation of both 6‐anti and 6‐syn enabled detailed discussion of the structure‐property relationship.

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Syn and Anti Metal Complexes of 24π Antiaromatic Bis(Dicarbonylrhodium(I))Dithiaamethyrin

Ishimaru

Takahashi

Mochizuki

et al. 2022

Chemistry An Asian Journal

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Homocarbaporphyrinoids: The m‐o‐m and p‐o‐p Terphenyl Embedded Expanded Porphyrin Analogues and Their Rh^I Complexes

Adinarayana

Das

Suresh

et al. 2019

Chemistry A European J

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Stable homocarbaporphyrinoids were successfully synthesized by incorporating the m‐o‐m and p‐o‐p terphenyl units into the porphyrin core. The distinct bonding modes of terphenyl in the macrocycle generated two structural isomers with two and four carbon atoms in the macrocyclic environment. The core was utilized to stabilize the RhI ion. The spectral and structural analyses revealed that the restricted (m‐o‐m) and allowed (p‐o‐p) conjugation in the macrocyclic core provide overall non‐aromatic characteristics both to the free bases and their complexes.

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Mechanistic Study on Ring‐Contracting Skeletal Rearrangement from Porphycene to Isocorrole by Experimental and Theoretical Methods

et al. 2020

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In this study, the ring contracting skeletal rearrangement reaction in one‐pot under basic conditions from octaethylporphycene to two types of isocorroles, i.e., the meso‐formyl and meso‐free forms, was confirmed and the reaction mechanism was proposed by the comparative analyses of the experimental and theoretical studies. The electron accepting nature of the porphycene and imine‐amine conversion of pyrrole rings make it possible to react with hydroxide ions and the following reaction to afford isocorroles. Based on this reaction, the valence of the compound as a ligand as well as the photochemical and electrochemical properties were dramatically changed.

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An Expanded Porphycene with High NIR Absorptivity That Stabilizes Two Different Kinds of Metal Complexes

Abstract: Scheme 1. Porphycene 1a,ethioporphycene 1b,b ronzaphyrin 2,a cetylene-cumulene porphycene 3,dibenzoporphycene 4,a nd expanded porphycene 5.

Cited by 4 publications

References 32 publications

Syn and Anti Metal Complexes of 24π Antiaromatic Bis(Dicarbonylrhodium(I))Dithiaamethyrin

Syn and Anti Metal Complexes of 24π Antiaromatic Bis(Dicarbonylrhodium(I))Dithiaamethyrin

Homocarbaporphyrinoids: The m‐o‐m and p‐o‐p Terphenyl Embedded Expanded Porphyrin Analogues and Their Rh^I Complexes

Mechanistic Study on Ring‐Contracting Skeletal Rearrangement from Porphycene to Isocorrole by Experimental and Theoretical Methods

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An Expanded Porphycene with High NIR Absorptivity That Stabilizes Two Different Kinds of Metal Complexes

Abstract: Scheme 1. Porphycene 1a,ethioporphycene 1b,b ronzaphyrin 2,a cetylene-cumulene porphycene 3,dibenzoporphycene 4,a nd expanded porphycene 5.

Cited by 4 publications

References 32 publications

Syn and Anti Metal Complexes of 24π Antiaromatic Bis(Dicarbonylrhodium(I))Dithiaamethyrin

Syn and Anti Metal Complexes of 24π Antiaromatic Bis(Dicarbonylrhodium(I))Dithiaamethyrin

Homocarbaporphyrinoids: The m‐o‐m and p‐o‐p Terphenyl Embedded Expanded Porphyrin Analogues and Their RhI Complexes

Mechanistic Study on Ring‐Contracting Skeletal Rearrangement from Porphycene to Isocorrole by Experimental and Theoretical Methods

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Product

Resources

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Homocarbaporphyrinoids: The m‐o‐m and p‐o‐p Terphenyl Embedded Expanded Porphyrin Analogues and Their Rh^I Complexes