TY - JOUR
T1 - Control of Assembly of Dihydropyridyl and Pyridyl Molecules via Directed Hydrogen Bonding
AU - Lü, Jian
AU - Han, Li-Wei
AU - Alsmail, Nada H.
AU - Blake, Alexander J.
AU - Lewis, William
AU - Cao, Rong
AU - Schroder, Martin
N1 - We thank EPSRC and the University of Nottingham for support. Financial support from the 973 Program (2011CB932504, 2012CB821705), NSFC (21331006, 21221001, 21101155, and 21203199), Fujian Key Laboratory of Nanomaterials (2006L2005), and Key Project from CAS are gratefully acknowledged. J.L. and M.S. thank the NSFC-RS for the International Exchanges Scheme (2011 China Costshare project based on NSFC 21001105) for financial support. J.L. acknowledges the Royal Society Sino-British Fellowship Trust for an Incoming Fellowship. N.H.A. thanks the Royal Commission for Jubail and Yanbu, Jubail University College, Kingdom of Saudi Arabia, for a PhD Scholarship. M.S. gratefully acknowledges receipt of an ERC Advanced Grant.Additional figures of IR, TGA, and PXRD data and crystallographic data in CIF format. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.5b00395.
PY - 2015/7/28
Y1 - 2015/7/28
N2 - The crystallization of two dihydropyridyl molecules, 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)benzene ([C40H24N10]·2DMF, 1·2DMF; DMF = dimethylformamide) and 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)phenylbenzene ([C46H28N10]·2DMF, 3·2DMF), and their respective oxidized pyridyl analogues, 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)benzene ([C40H20N10], 2) and 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)phenylbenzene ([C46H24N10]·DMF, 4·DMF), has been achieved under solvothermal conditions. The dihydropyridyl molecules are converted to their pyridyl products via in situ oxidative dehydrogenation in solution. The structures of the four molecules have been fully characterized by single crystal and powder X-ray diffraction. The oxidized pyridyl products, 2 and 4, are more elongated due to aromatization of the dihydropyridyl rings at each end of their parent molecules 1 and 3, respectively. The solid-state supramolecular structures of the pyridyl molecules are distinct from the dihydropyridyl molecules in terms of their hierarchical assembly via hydrogen bonding due to the loss of primary N–H hydrogen bond donors in the two electron oxidized tectons. Overall, the geometrically shorter molecules 1 and 3 display close-packed structures, whereas the more extended 2 and 4 assemble into more open supramolecular systems.
AB - The crystallization of two dihydropyridyl molecules, 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)benzene ([C40H24N10]·2DMF, 1·2DMF; DMF = dimethylformamide) and 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)phenylbenzene ([C46H28N10]·2DMF, 3·2DMF), and their respective oxidized pyridyl analogues, 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)benzene ([C40H20N10], 2) and 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)phenylbenzene ([C46H24N10]·DMF, 4·DMF), has been achieved under solvothermal conditions. The dihydropyridyl molecules are converted to their pyridyl products via in situ oxidative dehydrogenation in solution. The structures of the four molecules have been fully characterized by single crystal and powder X-ray diffraction. The oxidized pyridyl products, 2 and 4, are more elongated due to aromatization of the dihydropyridyl rings at each end of their parent molecules 1 and 3, respectively. The solid-state supramolecular structures of the pyridyl molecules are distinct from the dihydropyridyl molecules in terms of their hierarchical assembly via hydrogen bonding due to the loss of primary N–H hydrogen bond donors in the two electron oxidized tectons. Overall, the geometrically shorter molecules 1 and 3 display close-packed structures, whereas the more extended 2 and 4 assemble into more open supramolecular systems.
U2 - 10.1021/acs.cgd.5b00395
DO - 10.1021/acs.cgd.5b00395
M3 - Article
SN - 1528-7483
VL - 15
SP - 4219
EP - 4224
JO - Crystal Growth & Design
JF - Crystal Growth & Design
IS - 9
ER -