Lock-Arm Supramolecular Ordering: A Molecular Construction Set for Cocrystallizing Organic Charge Transfer Complexes
datasetposted on 10.12.2014, 00:00 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 Stoddart
Organic 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.