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Aromaticity and Chemical Bonding of Chalcogen‐Bonded Capsules Featuring Enhanced Magnetic Anisotropy
Author(s) -
Tzeli Demeter,
Petsalakis Ioannis D.,
Theodorakopoulos Giannoula,
Rahman FaizUr,
Ballester Pablo,
Rebek Julius,
Yu Yang
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000654
Subject(s) - chalcogen , polarizability , hydrogen bond , crystallography , chemistry , heteroatom , stacking , chemical shift , anisotropy , chemical bond , stereochemistry , molecule , organic chemistry , ring (chemistry) , physics , quantum mechanics
We present a theoretical study of chalcogen bonded container capsules ( A X +A X ) where X=O, S, Se, and Te, and their encapsulation complexes with n‐ C 9 H 20 ( n‐ C 9 H 20 @ A X +A X ). Both Se and Te encapsulation complexes have significant experimental and computed binding energies, analogous to the hydrogen bonded counterparts, while the S and O capsules and their encapsulation complexes show only weak binding energies, which are attributed to different types of bonding: chalcogen S⋅⋅⋅N bonds for S‐capsules and π–π stacking and weak hydrogen bonds for the O case. All A X +A X and C 9 H 20 @ A X +A X present unusually high magnetic anisotropies in their interiors. The 1 H NMR spectra of the encapsulation complexes display the proton signals of the encapsulated n‐ nonane highly upfield shifted, in agreement with the available experimental data for the Se capsule. We found that different factors contribute to the observed magnetic anisotropy of the capsule's interior: for the Te capsule the most important factor is Te's large polarizability; for the O analogue the inductive effects produced by the electronegative nature of the O and N heteroatoms; and for the S and Se capsules, the polarizability of the heteroatoms combines with electric field effects.