Tailor-made aromatic porphyrinoids with NIR absorption

Abstract

The highlight of this article is the recent progress in the state-of the art synthetic design and isolation of artificial porphyrinoids by swapping pyrrole component(s) with diverse functionalized pyrrolic(heterocyclic)/carbacycle building...

An extended quinoid molecule based on bis(thiophene-diketopyrrolopyrrole) with balanced ambipolar semiconducting properties and strong near-infrared absorption

“…Currently, conjugated small molecules/polymers showing semiconducting properties and strong absorption in the near-infrared region (NIR, >750 nm) simultaneously are of great interest, because of their potential applications in organic solar cells, 1 organic thin-film transistors, 2 organic photodetectors, 3–5 and biological and medical applications. 6–12 To obtain organic semiconductors with NIR absorption, the basic principle in molecular design is to reduce the band gap between the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) energy levels. 11 For such a purpose, various strategies, including construction of electron donor–acceptor conjugated small molecules/polymers, extension of the conjugation length and reduction of bond length alternation, have been proposed and extensively investigated.…”

“…11 For such a purpose, various strategies, including construction of electron donor–acceptor conjugated small molecules/polymers, extension of the conjugation length and reduction of bond length alternation, have been proposed and extensively investigated. 1–12…”

Synthesis and Studies of Di(p‐Benzi)Decaphyrin and Di(9,10‐Anthracenyl)Decaphyrin

“…Expanded porphyrinoids [1,2] contains pyrroles [3] /heterocycles [4] /carbacycles [5] linked together either directly or through one or more methine carbon atoms in such a manner that the internal ring pathway contains a minimum of 17 atoms. These macrocycles have received significant attention over few decades because of their diverse applications in materials science, [6] chemistry, [7,8] medicine [9] and biology [10] .…”

“…[10] The expanded macrocycles have been used as non-linear optical materials, [11] sensitizers for PDT, [12,13] PTT, models to study different types of aromaticity, [14,15] radiation therapy enhancers and contrasting agents. Expanded porphyrinoids containing more than 18π electrons in conjugation are very useful as NIR absorbing materials [4] and their large cavity sizes makes them very attractive ligands in coordination chemistry. [16,17] The properties of expanded porphyrinoids can be finely tuned by suitable modifications such as increasing the number of heterocycles/ carbacycles or methine-linkages in the porphyrinoid framework and the presence of different inner core-atoms helps in formation of novel, unusual coordination complexes.…”

NIR Absorbing Aromatic E-Ethylene Bridged Hexaphyrins (2.1.1.2.1.1): Synthesis, Characterization, and Protonation Studies

“…Aromaticity reversal in expanded porphyrins is usually triggered by structural modification, redox chemistry, NH tautomerization, and singlet and triplet excited electronic states. , The electrochemical redox behavior of 8 fascinated us and led us to unravel aromaticity switching upon reduction. Thus, NaBH 4 reduction of macrocycle 8 under inert atmosphere conditions at ambient temperature was tried; however, 8 remained chemically unreactive toward NaBH 4 (Scheme S3).…”