ja509442t_si_008.cif (257.04 kB)
Lock-Arm Supramolecular Ordering: A Molecular Construction Set for Cocrystallizing Organic Charge Transfer Complexes
dataset
posted on 2014-12-10, 00:00 authored by Anthea
K. Blackburn, Andrew C.-H. Sue, Alexander K. Shveyd, Dennis Cao, Alok Tayi, Ashwin Narayanan, Brian
S. Rolczynski, Jodi M. Szarko, Ozgur A. Bozdemir, Rie Wakabayashi, Jessica A. Lehrman, Bart Kahr, Lin X. Chen, Majed
S. Nassar, Samuel I. Stupp, J. Fraser StoddartOrganic
charge transfer cocrystals are inexpensive, modular, and solution-processable
materials that are able, in some instances, to exhibit properties
such as optical nonlinearity, (semi)conductivity, ferroelectricity,
and magnetism. Although the properties of these cocrystals have been
investigated for decades, the principal challenge that researchers
face currently is to devise an efficient approach which allows for
the growth of high-quality crystalline materials, in anticipation
of a host of different technological applications. The research reported
here introduces an innovative design, termed LASOlock-arm
supramolecular orderingin the form of a modular approach for
the development of responsive organic cocrystals. The strategy relies
on the use of aromatic electronic donor and acceptor building blocks,
carrying complementary rigid and flexible arms, capable of forming
hydrogen bonds to amplify the cocrystallization processes. The cooperativity
of charge transfer and hydrogen-bonding interactions between the building
blocks leads to binary cocrystals that have alternating donors and
acceptors extending in one and two dimensions sustained by an intricate
network of hydrogen bonds. A variety of air-stable, mechanically robust,
centimeter-long, organic charge transfer cocrystals have been grown
by liquid–liquid diffusion under ambient conditions inside
72 h. These cocrystals are of considerable interest because of their
remarkable size and stability and the promise they hold when it comes
to fabricating the next generation of innovative electronic and photonic
devices.