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Halogen‐Bonded Supramolecular Capsules in the Solid State, in Solution, and in the Gas Phase
Author(s) -
Dumele Oliver,
Schreib Benedikt,
Warzok Ulrike,
Trapp Nils,
Schalley Christoph A.,
Diederich François
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201610884
Subject(s) - supramolecular chemistry , acceptor , halogen bond , chemistry , molecule , benzene , hydrogen bond , halogen , electrospray ionization , solid state , crystallography , crystal structure , mass spectrometry , organic chemistry , physics , alkyl , chromatography , condensed matter physics
Supramolecular capsules were assembled by neutral halogen bonding (XB) and studied in the solid state, in solution, and in the gas phase. The geometry of the highly organized capsules is shown by an X‐ray crystal structure which features the assembly of two XB hemispheres, geometrically rigidified by H‐bonding to eight MeOH molecules and encapsulation of two benzene guests. To enhance capsular association strength, tuning the XB donor is more efficient than tuning the XB acceptor, due to desolvation penalties in protic solvents, as shown for a tetraquinuclidine XB acceptor hemisphere. With a tetra(iodoethynyl) XB donor and a tetralutidine XB acceptor, the association in deuterated benzene/acetone/methanol 70:30:1 at 283 K reaches K a =(2.11±0.39)×10 5 m −1 (Δ G =−6.9±0.1 kcal mol −1 ). The stability of the XB capsules in the gas phase was confirmed by electrospray ionization mass spectrometry (ESI‐MS). A new guest binding site was uncovered within the elongated iodoethynyl capsule.