Inherently chiral helicene-substituted thioalkyl porphyrazine complexes: synthesis and electronic and chiroptical properties

Year: 2022

Authors: Belviso S., Marsico G., Franzini R., Villani C., Abbate S., Longhi G.

Autors Affiliation: Univ Basilicata, Dipartimento Sci, Viale Ateneo Lucano 10, I-85100 Potenza, Italy; Univ Roma La Sapienza, Dipartimento Chim & Tecnol Farmaco, Piazzale Aldo Moro 5, I-00185 Rome, Italy; Univ Brescia, Dipartimento Med Mol & Traslaz, Viale Europa 11, I-25123 Brescia, Italy; INO CNR Unit Brescia, CSMT Via Branze 45, I-25123 Brescia, Italy.

Abstract: The chiral Ni(ii) and Pd(ii) complexes of [6]helicene thioethyl porphyrazine have been synthesized and their spectroscopic, electrochemical, and chiroptical properties have been investigated by experimental and computational analyses. In these compounds, the tetrapyrrole macrocycle is beta-substituted with an inherently chiral extended aromatic moiety potentially suitable to establish attractive pi-pi interactions with nanocarbons and endowed with helical chirality, both features providing interesting properties for optoelectronic applications. Experimental and density functional theory computational analyses highlight the presence of HOMO-LUMO charge-transfer transitions between the helicene moiety and the porphyrazine macrocycle. These compounds behave as mono-substituted push-pull systems without any typical electron-withdrawing or electron-donating groups and thus appear promising for optoelectronics. The enantiomers of the Ni(ii) complex have been separated by chiral HPLC and their absolute configuration has been established by density functional theory computational analysis of electronic circular dichroism spectra. The magnetic circular dichroism spectrum of this complex has also been recorded providing better insight into its electronic structure.

Journal/Review: DALTON TRANSACTIONS

Volume: 51 (43)      Pages from: 16453  to: 16464

More Information: S. B. gratefully acknowledges the financial support from the European Union NextGenerationEU and Italian Ministry of University and Research (MUR) National Recovery and Resilience Plan (NRRP) Program Strengthening of research structures and creation of R&D innovation ecosystems, [Tech4You – Technologies for climate change adaptation and quality of life improvement Project, grant n. ECS_0000009]. GL and SA received financial support from MUR through the PRIN program [PRIN 2017, project Physico-chemical Heuristic Approaches: Nanoscale Theory of Molecular Spectroscopy (PHANTOMS), prot. 2017A4XRCA].
KeyWords: Organic Photovoltaics; Circular-dichroism; Free-base; Push-pull; Electrochemistry; Phthalocyanines; Semiconductor; Spectroscopy; Performance; Porphyrins
DOI: 10.1039/d2dt02665a

Citations: 4
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