Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Computational Insight into the Electronic Structure and Absorption Spectra of Lithium Complexes of N-Confused Tetraphenylporphyrin
Δημιουργός/Συγγραφέας:	[EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter [EL] Πετσαλάκης, Ιωάννης Δ.[EN] Petsalakis, Ioannis D. [EL] Θεοδωρακοπούλου, Γιαννούλα[EN] Theodorakopoulos, Giannoula
Εκδότης:	American Chemical Society
Τόπος έκδοσης:	WASHINGTON
Ημερομηνία:	2011-10-27
Γλώσσα:	Αγγλικά
ISSN:	1089-5639
DOI:	10.1021/jp204298q
Περίληψη:	The present work is a theoretical investigation on lithium complexes of N-confused tetraphenylporphyrins (aka inverted) employing density functional theory (DFT) and tune dependent DFT, using the B3LYP, CAM-B3LYP, and M06-2X functionals in conjunction with the 6-31G(d,p) basis set. The purpose of the present study is to calculate the electronic structure and the bonding of the complexes to explain the unusual coordination environment in which Li is found experimentally and how the Li binding affects the Q and the Soret bands. The calculations show that, unlike a typical tetrahedral Li(+) cation, this Li forms a typical bond with one N and interacts with the remaining two N atoms, and it is located in the right place to form an agostic-like interaction with the internal C atom. The reaction energy, the enthalpy for the formation of the lithium complexes of N-confused porphyrins, and the effect Of solvation are also calculated. The insertion of Li into N-confused porphyrin, in the presence of tetrahydrofuran, is exothermic with:a reaction energy calculated lobe as high as 724 kcal/mol using the lithium bis(trimethylsilyl)amide reagent. Finally, there is agreement in the general shape among the vis-UV spectra determined with different functionals and the experimentally available ones. The calculated geometries are in agreement with crystallographic data, where available.
Τίτλος πηγής δημοσίευσης:	Journal of Physical Chemistry A
Τόμος/Κεφάλαιο:	115
Τεύχος:	42
Σελίδες:	11749-11760
Θεματική Κατηγορία:	[EL] Χημεία (Γενικά)[EN] Chemistry (General) [EL] Φυσική[EN] Physics
Λέξεις-Κλειδιά:	Chemistry, Physical Physics, Atomic, Molecular & Chemical
Αξιολόγηση από ομότιμους (peer reviewed):	Ναι
EU Grant identifier:	info:eu-repo/grantAgreement/EC/FP7/201729
Κάτοχος πνευματικών δικαιωμάτων:	© AMER CHEMICAL SOC
Ηλεκτρονική διεύθυνση περιοδικού (link) :	http://pubs.acs.org/jpca
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο