Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Abstract

Treatment of a meso-diarylporphyrin with PhI(OAc) 2 in the presence of BF 3 • OEt 2 and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso-meso β-β doubly-fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000 nm. It has a low HOMO-LUMO gap owing to expanded and low-symmetry π-planes.

Stepwise Oxidative C–C Coupling and/or C–N Fusion of Zn(II) meso-Pyridin-2-ylthio-porphyrins

“…As compared to their unfused precursors, the resulting extended structures demonstrate important modification of their electronic properties (bathochromic shift of their absorption/emission spectrum, two-photon cross-sectional increase, and decrease of the HOMO–LUMO gap among others) and find applications in photovoltaic cells, , molecular electronics, photodynamic therapy, non-linear optical materials, and near-IR electroluminescence displays, just to mention a few . More specifically with porphyrinoids, C–C and C–N fusion reactions have been performed starting with halogenated precursors, − using transition metals (silver, iron, , copper, palladium, scandium, gold), organic oxidants (DDQ, PIDA, PIFA...), and reducing agents such as P­(OEt 3 ), by heating , or S N Ar reaction . These syntheses are often performed under harsh conditions (oxidants in large excess, high temperature, acidic medium, etc.).…”

Redox‐Mediated Single‐Molecule Transistor with A Subthreshold Swing Down To 120 mV Decade−1

“…When adding water gradually to the OSTPP solution, we observed a positive shift of the complete two reduction waves until they coincided [ 40 ] shown in Figure S2 (Supporting Information). The observed redox behavior of OSTPP is attributed to the electrochemical‐electrochemical (EE) reduction mechanism [ 41 ] of typical porphyrinquinone [ 42,43 ] in aprotic organic solvents. As shown in Figure S3 (Supporting Information), the control experiments with pure solvent indicate that electrodes and electrolytic cell are clean.…”

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

“…350.10 displayed strong panchromatic absorption between 300 and 1000 nm, with a large maximum at 724 nm, and possessed a significantly reduced electrochemical HOMO–LUMO gap relative to the monomeric quinone. 653 …”

“…The singly fused diporphyrin quinone 350.10 was reported by Yamashita, Sugiura et al The compound was obtained in low yield in a tandem PIFA-induced oxidation of a 5,15-diarylporphyrin along with the expected monomeric dioxoporphodimethane. 350.10 displayed strong panchromatic absorption between 300 and 1000 nm, with a large maximum at 724 nm, and possessed a significantly reduced electrochemical HOMO–LUMO gap relative to the monomeric quinone …”