Engineering crystals of dendritic molecules.
A detailed single-crystal X-ray study of conformationally flexible sulfonimide-based dendritic molecules with systematically varied molecular architectures was undertaken. Thirteen crystal structures reported in this work include 9 structures of the second-generation dendritic sulfonimides decorated with different aryl groups, 2 compounds bearing branches of both second and first generation, and 2 representatives of the first generation. Analysis of the packing patterns of 9 compounds bearing second-generation branches shows that despite their lack of strong directive functional groups there is a repeatedly reproduced intermolecular interaction mode consisting in an anchor-type packing of complementary second-generation branches of neighbouring molecules. The observed interaction tolerates a wide range of substituents in meta- and para-positions of the peripheral arylsulfonyl rings. Quantum chemical calculations of the molecule-molecule interaction energies agree at the qualitative level with the packing preferences found in the crystalline state. The calculations can therefore be used as a tool to rationalize and predict molecular structures with commensurate and non-commensurate branches for programming of different packing modes in crystal.
Lukin
Oleg
O
Institute of Polymers, Department of Materials, HCI G527, and Organic Chemistry Laboratory, HCI G301, Eidgenössische Technische Hochschule, 8093 Zurich, Switzerland. o.lukin@ukrorgsynth.com
Schubert
Dirk
D
Müller
Claudia M
CM
Schweizer
W Bernd
WB
Gramlich
Volker
V
Schneider
Julian
J
Dolgonos
Grygoriy
G
Shivanyuk
Alexander
A