Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Tuning the Photophysical Properties of Nickel and Zinc Complexes of N-Confused Tetraphenylporphyrin via Trans-Cis Isomerization
Δημιουργός/Συγγραφέας:	Papamichalis, Eleftherios [EL] Πετσαλάκης, Ιωάννης Δ.[EN] Petsalakis, Ioannis D. [EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter
Ημερομηνία:	2025-06-25
Γλώσσα:	Αγγλικά
ISSN:	1089-5639 1520-5215
DOI:	10.1021/acs.jpca.5c02035
Άλλο:	40566832
Περίληψη:	Porphyrins are detected in many biological systems and have significant roles in some important artificial systems, while the N-confused porphyrins present very interesting photophysical and chemical properties, which differ from those observed in porphyrins. In the present study, metal (M) complexes of tetraphenylporphyrin (TPP), N-confused TPP (NCTPP), and the ethenyl-pyrazine derivative of NCTPP (NCTPP-p), i.e., M-TPP, M-NCTPP, and M-NCTPP-p, where M = ZnII and NiII, were studied via density functional theory (DFT) and TD-DFT calculations. The photophysical properties of molecules and their absorption spectra are studied. It has been found that the MII affects the relative stability of the M-NCTPP and M-NCTPP-p tautomers, resulting in different tautomers having the lowest energy structure, while for the M-NCTPP-p molecule, there are cis isomers, which are lower in energy than the corresponding trans isomers due to the van der Waals interactions. The global minima of the nickel complexes have the H atom of a reversed pyrrole attached to C (a), while the zinc complexes have the H atom outside of the porphyrin core attached to N (b). For M-NCTPP-p, the global minimums are a.cis (NiII) and b.trans (ZnII). The absorption main peaks of M-NCTPP-p are red-shifted compared to M-NCTPP up to 80(135) nm for the Soret(Q) bands. The different isomers present shifts of their main absorption peaks up to 50(180) nm. Additionally, the vertical de-excitation energies from selected excited states are also investigated. Overall, the selection of the metal and the peripheral group lead to different lowest values in the energy structure, affect its UV-vis absorption spectrum, and thus they tune the photophysical properties of the M-NCTPP complexes.
Τίτλος πηγής δημοσίευσης:	The journal of physical chemistry. A
Θεματική Κατηγορία:	[EL] Φασματοσκοπία[EN] Spectroscopy [EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry [EL] Οργανική χημεία[EN] Organic chemistry [EL] Ανόργανη χημεία[EN] Inorganic chemistry
Λέξεις-Κλειδιά:	absorption energy metals molecular structure pyrroles
Κάτοχος πνευματικών δικαιωμάτων:	© 2025 The Authors. Published by American Chemical Society
Όροι και προϋποθέσεις δικαιωμάτων:	This publication is open, licensed under CC-BY 4.0.
Ηλεκτρονική διεύθυνση στον εκδότη (link):	https://doi.org/10.1021/acs.jpca.5c02035
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο