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Panchromatic Light Harvesting and Stabilizing Charge‐Separated States in Corrole–Phthalocyanine Conjugates through Coordinating a Subphthalocyanine
Author(s) -
Berna Beatrice Berionni,
Platzer Benedikt,
Wolf Maximiliam,
Lavarda Giulia,
Nardis Sara,
Galloni Pierluca,
Torres Tomás,
Guldi Dirk M.,
Paolesse Roberto
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001442
Subject(s) - photoexcitation , photochemistry , intramolecular force , chemistry , absorption (acoustics) , electron transfer , phthalocyanine , fluorescence , conjugate , materials science , atomic physics , stereochemistry , organic chemistry , excited state , physics , mathematical analysis , mathematics , quantum mechanics , composite material
Owing to the electron‐donating and ‐accepting nature of corroles (Corr) and phthalocyanines (Pc), respectively, we designed and developed two novel covalently linked Corr‐Pc conjugates. The synthetic route allows the preparation of the target conjugates in satisfying yields. Comprehensive steady‐state absorption, fluorescence, and electrochemical assays enabled insights into energy and electron‐transfer processes upon photoexcitation. Coordinating a pyridine‐appended subphthalocyanine (SubPc) to the Pc of the conjugate sets up the ways and means to realize the first example of an array composed by three different porphyrinoids, which drives a cascade of energy and charge‐transfer processes. Importantly, the SubPc assists in stabilizing the charge‐separated state, that is, one‐electron oxidized Corr and the one electron‐reduced Pc, upon photoexcitation by means of a reductive charge transfer to the SubPc. To the best of our knowledge, this is the first case of an intramolecular oxidation of a Corr within electron‐donor–acceptor conjugates by means of just photoexcitation. Moreover, the combination of Corr, Pc, and SubPc guarantees panchromatic absorption across the visible range of the solar spectrum, with the SubPc covering the „green gap“ that usually affects porphyrinoids.