Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Chalcogen bonding and hydrophobic effects force molecules into small spaces
Δημιουργός/Συγγραφέας:	Rahman, Faiz-Ur [EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter [EL] Πετσαλάκης, Ιωάννης Δ.[EN] Petsalakis, Ioannis D. [EL] Θεοδωρακοπούλου, Γιαννούλα[EN] Theodorakopoulos, Giannoula Ballester, Pablo Rebek, Julius Yu, Yang
Εκδότης:	ACS Publications
Ημερομηνία:	2020-03-25
Γλώσσα:	Αγγλικά
ISSN:	0002-7863 1520-5126
DOI:	10.1021/jacs.0c01290
Άλλο:	32125842
Περίληψη:	Supramolecular capsules are desirable containers for the study of molecular behavior in small spaces and offer applications in transport, catalysis, and material science. We report here the use of chalcogen bonding to form container assemblies that are stable in water. Cavitands 1-3 functionalized with 2,1,3-benzoselenadiazole walls were synthesized in good yield from resorcin[4]arenes. The solid-state single-crystal X-ray structure of 3 showed a dimeric assembly cemented together through multiple Se···N chalcogen bonds. Binding of hydrophobic and amphiphilic guests in D2O was investigated by 1H NMR methods and revealed host-guest assemblies of 1:1, 2:1, and 2:2 stoichiometries. Small guests such as n-hexane or cyclohexane assembled as 2:2 capsular complexes, larger guests like cyclohexane carboxylic acid or cyclodecane formed 1:1 cavitand complexes, and longer linear guests like n-dodecane, cyclohexane carboxylic acid anhydride, and amides created 2:1 capsular complexes. The 2:1 complex of the capsule with cyclohexane carboxylic acid anhydride was stable over 2 weeks, showing that the seam of chalcogen bonds is "waterproof". Selective uptake of cyclohexane over benzene and methyl cyclohexane over toluene was observed in aqueous solution with the capsule. Hydrophobic forces and hydrogen-bonding attractions between guest molecules such as 3-methylbutanoic acid stabilized the assemblies in the presence of the competing effects of water. The high polarizability and modest electronegativity of Se provide a capsule lining complementary to guest C-H bonds. The 2,1,3-benzoselenadiazole walls impart an unusually high magnetic anisotropy to the capsule environment, which is supported by density functional theory calculations.
Τίτλος πηγής δημοσίευσης:	Journal of the American Chemical Society
Τόμος/Κεφάλαιο:	142
Τεύχος:	12
Σελίδες:	5876–5883
Θεματική Κατηγορία:	[EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry [EL] Χημεία (Γενικά)[EN] Chemistry (General) [EL] Φασματοσκοπία[EN] Spectroscopy
Λέξεις-Κλειδιά:	Capsular assembly Supramolecular capsules Synthesis Chalcogen bonging
Κάτοχος πνευματικών δικαιωμάτων:	Copyright © 2020 American Chemical Society
Ηλεκτρονική διεύθυνση στον εκδότη (link):	https://pubs.acs.org/doi/10.1021/jacs.0c01290
Ηλεκτρονική διεύθυνση περιοδικού (link) :	https://pubs.acs.org/journal/jacsat
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο