Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	The role of electric field, peripheral chains, and magnetic effects on significant 1H upfield shifts of the encapsulated molecules in chalcogen-bonded capsules
Δημιουργός/Συγγραφέας:	[EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter [EL] Πετσαλάκης, Ιωάννης Δ.[EN] Petsalakis, Ioannis D. [EL] Θεοδωρακοπούλου, Γιαννούλα[EN] Theodorakopoulos, Giannoula Rahman, Faiz-Ur Yu, Yang Rebek, Julius
Ημερομηνία:	2021-09-15
Γλώσσα:	Αγγλικά
DOI:	10.1039/d1cp02277f
Άλλο:	34524297
Περίληψη:	The chalcogen-bonded homo-cavitand and hetero-cavitand AY+AY' capsules (Y, Y' = Se, Te), as well as their encapsulated complexes with one or two guest molecules have been studied theoretically via density functional theory (DFT), while the 1H NMR spectra of the homo-cavitand encapsulated complexes (in ASe+ASe) have been measured experimentally. There is excellent agreement between theoretical and experimental spectra. In all cases, we found significant 1H upfield shifts which are more intense in the ASe+ASe cage compared to the ATe+ATe and ASe+ATe cages. The non-uniform electron distribution which gives rise to an inherent electric field and a non-zero electric dipole moment of the encapsulated complexes, the induced electric field effects, the magnetic anisotropy which is enhanced due to the polarizability of chalcogen atoms, and the peripheral chains, which are responsible for the solubility of the cages, increase the upfield shifts of 1H of the encapsulated molecules; the peripheral chains lead to an increase of the upfield shifts by up to 1.8 ppm for H of the rim and up to 1.2 ppm for the terminal H in the interior of the cage. Hence, substantial 1H upfield chemical shifts of the guests in these capsules are consequences of (i) the enhanced aromaticity of the walls of the capsules due to the polarizability of chalcogen atoms, (ii) the induced and inherent electric field effects, and (iii) the peripheral chains.
Τίτλος πηγής δημοσίευσης:	Physical chemistry chemical physics : PCCP
Τόμος/Κεφάλαιο:	23
Τεύχος:	35
Σελίδες:	19647–19658
Θεματική Κατηγορία:	[EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry
Λέξεις-Κλειδιά:	Noncovalent interactions Peripheral chains Electric fields Peripheral chains Encapsulated molecules Chalcogen bonded capsules
EU Grant identifier:	KE 17034 21801164 22071144 13-G210- 19-230
Όροι και προϋποθέσεις δικαιωμάτων:	Open access article.
Σημειώσεις:	DT acknowledges the National and Kapodistrian University of Athens, Special Accounts for Research Grants for supporting this work through the project ‘‘SONFM’’ (KE 17034). YY thanks the National Natural Science Foundation of China (No. 21801164 and 22071144), Shanghai University (No. 13-G210- 19-230) and the Program for Professor of Special Appointment (Dongfang Scholarship) of the Shanghai Education Committee.
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο