The phenyl–iron complex of 5,10,15-tritolylcorrole was prepared by reaction of the starting chloro–iron complex with phenylmagnesium bromide in dichloromethane. The organometallic complex was fully characterized by a combination of spectroscopic methods, X-ray crystallography, and density functional theory (DFT) calculations. All of these techniques support the description of the electronic structure of this phenyl–iron derivative as a low-spin iron(IV) coordinated to a closed-shell corrolate trianion and to a phenyl monoanion. Complete assignments of the 1H and 13C NMR spectra of the phenyl–iron derivative and the starting chloro–iron complex were performed on the basis of the NMR spectra of the regioselectively β-substituted bromo derivatives and the DFT calculations.

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Perovskite solar cells (PSCs) represent nowadays a promising starting point to develop a new efficient and low-cost photovoltaic technology due to the demonstrated power conversion efficiency (PCE) exceeding 25% on small area devices. However, best reported devices suffer from stability issue under real working conditions thus slowing down the race for the commercialization. In particular, the hole transporting material commonly employed in mesoscopic n-i-p PSCs (nip-mPSCs), namely spiro-OMeTAD, is strongly corrupted when subjected to temperatures above 70 °C due to intrinsic thermal instability and because of the dopant employed to improve the hole mobility. In this work, the novel use of a copper-based corrole as HTM is proposed to improve the device thermal stability of nip-mPSCs under prolonged 85 °C stress conditions. Corrole-based devices show remarkable PCE above 16% by retaining more than 65% of the initial PCE after 1000 h of thermal stress, while spiro-OMeTAD cells abruptly lose more than 60% after the first 40 h. Once scaled-up to large area modules, the proposed device structure can truly represent a possible way to pass thermal stress tests proposed by IEC-61646 standards and, not less importantly, the high temperature required by the lamination process for panel production.

Owing to the electron-donating and-accepting nature of corroles (Corr) and phthalocyanines (Pc), respectively,w ed esigned and developed two novel covalently linked Corr-Pc conjugates.T he synthetic route allows the preparation of the target conjugatesi ns atisfying yields. Comprehensives teady-state absorption, fluorescence, and electrochemical assayse nabled insights into energya nd electron-transfer processes upon photoexcitation. Coordinating ap yridine-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,w hichd rives ac ascade of energy and charge-transfer processes. Importantly,t he SubPc assists in stabilizing the charge-separated state, that is, one-electron oxidized Corr and the one electron-reduced Pc,u pon photoexcitation by means of ar eductive charget ransfer to the SubPc. To the best of our knowledge, this is the first case of an intramolecular oxidation of aC orr within electron-donor-acceptorc onjugates by means of just photoexcitation. Moreover,t he combination of Corr,P c, and SubPc guarantees panchromatic absorption across the visible rangeo ft he solar spectrum, with the SubPc covering the "green gap" that usually affects porphyrinoids.