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- W2968357189 abstract "Abstract A [2+2+1] cyclization strategy of bis(alkynyl)porphyrin using low‐valent titanium species, generated in situ, afforded phosphole‐fused dehydropurpurins for the first time. The systematic investigations on the electronic properties of the dehydropurpurins revealed their unique features owing to the oxidation states of the phosphorus atom on the fused phosphole ring. The phosphole P=O and P=S derivatives were found to possess high electron‐accepting character derived from phosphorus(V) centers without the contribution of 24π antiaromatic character, suggesting their potential utility as electron‐accepting materials. In contrast, the phosphorus(III) derivatives revealed different optical and electrochemical properties arising from both 18π aromatic and 24π antiaromatic networks including the lone pair of the phosphorus(III) atom. Overall, the oxidation state of the phosphorus atom has a clear impact on the whole electronic properties, demonstrating the advantages of chemical modifications of the phosphorus center for creating an exotic π‐system. The application of titanium‐mediated [2+2+1] cyclization to porphyrins is highly promising for expanding a world of heterole‐fused porphyrinoids." @default.
- W2968357189 created "2019-08-22" @default.
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- W2968357189 date "2019-09-19" @default.
- W2968357189 modified "2023-10-17" @default.
- W2968357189 title "Phosphole‐Fused Dehydropurpurins via Titanium‐Mediated [2+2+1] Cyclization Strategy" @default.
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- W2968357189 doi "https://doi.org/10.1002/chem.201903269" @default.
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