title: Control of Assembly of Dihydropyridyl and Pyridyl Molecules via Directed Hydrogen Bonding.
abstract: 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,2and4, are more elongated due to aromatization of the dihydropyridyl rings at each end of their parent molecules1and3, 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 molecules1and3display close-packed structures, whereas the more extended2and4assemble into more open supramolecular systems.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, 350002 Fujian, P. R. China ; School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K.
authors.forename: Jian
authors.initials: J
authors.lastname: Lü
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, 350002 Fujian, P. R. China ; School of Chemistry and Chemical Engineering, Nantong University , Nantong, 226019 Jiangsu, P. R. China.
authors.forename: Li-Wei
authors.initials: LW
authors.lastname: Han
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K.
authors.forename: Nada H
authors.initials: NH
authors.lastname: Alsmail
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K.
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, 350002 Fujian, P. R. China.
authors.forename: Rong
authors.initials: R
authors.lastname: Cao
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K. ; School of Chemistry, University of Manchester , Manchester M13 9PL, U.K.
authors.forename: Martin
authors.initials: M
authors.lastname: Schröder