TY - JOUR
T1 - Supramolecular chromotropism of the crystalline phases of 4,5,6,7-tetrafluorobenzo-2,1,3-telluradiazole
AU - Cozzolino, Anthony F.
AU - Whitfield, Pamela S.
AU - Vargas-Baca, Ignacio
N1 - Copyright:
Copyright 2011 Elsevier B.V., All rights reserved.
PY - 2010/12/8
Y1 - 2010/12/8
N2 - The remarkable effect that secondary bonding interactions can have on the macroscopic properties of a material is illustrated by two polymorphs of the title compound. The phase which is most stable under ambient pressure and temperature consists of puckered supramolecular ribbon polymers assembled by Te - N secondary bonding interactions and displays a characteristic red-orange color. A second yellow phase consists of ribbons with alternating short and long intermolecular Te - N secondary bonding distances and is metastable; at 127 °C the material undergoes an exothermic irreversible transition to the red polymorph. A third phase consists of pyridine-solvated supramolecular dimers; it is also yellow and transforms into the red phase after the crystals effloresce. Computational DFT studies indicate that the observed changes in optical properties are related to intermolecular mixing of π orbitals enabled by the supramolecular interactions and the symmetry of the supramolecular synthon.
AB - The remarkable effect that secondary bonding interactions can have on the macroscopic properties of a material is illustrated by two polymorphs of the title compound. The phase which is most stable under ambient pressure and temperature consists of puckered supramolecular ribbon polymers assembled by Te - N secondary bonding interactions and displays a characteristic red-orange color. A second yellow phase consists of ribbons with alternating short and long intermolecular Te - N secondary bonding distances and is metastable; at 127 °C the material undergoes an exothermic irreversible transition to the red polymorph. A third phase consists of pyridine-solvated supramolecular dimers; it is also yellow and transforms into the red phase after the crystals effloresce. Computational DFT studies indicate that the observed changes in optical properties are related to intermolecular mixing of π orbitals enabled by the supramolecular interactions and the symmetry of the supramolecular synthon.
UR - http://www.scopus.com/inward/record.url?scp=78650118929&partnerID=8YFLogxK
U2 - 10.1021/ja107252f
DO - 10.1021/ja107252f
M3 - Article
C2 - 21070032
AN - SCOPUS:78650118929
VL - 132
SP - 17265
EP - 17270
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 48
ER -