title: Exceptional thermal stability in a supramolecular organic framework: porosity and gas storage.
abstract: Reaction of β-amino-β-(pyrid-4-yl)acrylonitrile with the aromatic dicarboxaldehydes 9,10-bis(4-formylphenyl)anthracene and terephthalaldehyde affords the dihydropyridyl products 9,10-bis(4-((3,5-dicyano-2,6-dipyridyl)dihydropyridyl)phenyl)anthracene (L(1)) and 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)benzene (L(2)), respectively. In the solid state [L(1)]·2.5DMF·3MeOH (SOF-1) crystallizes in the monoclinic space group P2(1)/c and forms a 3D stable supramolecular organic framework via strong N-H···N(py) hydrogen bonds and π-π interactions. The material incorporates pyridyl-decorated channels and shows permanent porosity in the solid state. The pore volumes of the desolvated framework SOF-1a calculated from the N(2) isotherm at 125 K and the CO(2) isotherm at 195 K are 0.227 and 0.244 cm(3) g(-1), respectively. The N(2) absorption capacity of SOF-1a at 77 K is very low, with an uptake of 0.63 mmol g(-1) at 1 bar, although saturation N(2) adsorption at 125 K is 6.55 mmol g(-1) (or 143 cm(3) g(-1)). At ambient temperature, SOF-1a shows significant CO(2) adsorption with approximately 3 mol of CO(2) absorbed per mole of host at 16 bar and 298 K, corresponding to 69 cm(3) g(-1) at STP. SOF-1a also adsorbs significant amounts of C(2)H(2), with an uptake of 124 cm(3) (STP) g(-1) (5.52 mmol g(-1)) at 1 bar at 195 K. Methane uptake at 195 K and 1 bar is 69 cm(3) (STP) g(-1). Overall, gas adsorption measurements on desolvated framework SOF-1a reveal not only high capacity uptakes for C(2)H(2) and CO(2), compared to other crystalline molecular organic solids, but also an adsorption selectivity in the order C(2)H(2) > CO(2) > CH(4) > N(2). Overall, C(2)H(2)(270 K)/CH(4)(273 K) selectivity is 33.7 based on Henry's Law constant, while the C(2)H(2)(270 K)/CO(2)(273 K) ratio of uptake at 1 bar is 2.05. The less bulky analogue L(2) crystallizes in the triclinic space group P1 as two different solvates [L(2)]·2DMF·5C(6)H(6) (S2A) and [L(2)]·2DMF·4MeOH (S2B) as pale yellow tablets and blocks, respectively. Each L(2) molecule in S2A participates in two N-H···O hydrogen bonds between dihydropyridyl rings and solvent DMF molecules. Packing of these layers generates 1D nanochannels along the crystallographic a and b axes which host DMF and benzene molecules. In S2B, each L(2) ligand participates in hydrogen bonding via an N-H···O interaction between the N-H of the dihydropyridyl ring and the O of a MeOH and also via an N···H-O interaction between the N center of a pyridine ring and the H-O of a second MeOH molecule. The presence of the L(2)-HOMe hydrogen bonds prevents ligand-ligand hydrogen bonding. As a result, S2B crystallizes as one-dimensional chains rather than as an extended 3D network. Thermal removal of solvents from S2A results in conversion to denser phase S2C which shows no effective permanent porosity.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
authors.forename: Wenbin
authors.initials: W
authors.lastname: Yang
authors.forename: Alex
authors.initials: A
authors.lastname: Greenaway
authors.forename: Xiang
authors.initials: X
authors.lastname: Lin
authors.forename: Ryotaro
authors.initials: R
authors.lastname: Matsuda
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.forename: Claire
authors.initials: C
authors.lastname: Wilson
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.forename: Peter
authors.initials: P
authors.lastname: Hubberstey
authors.forename: Susumu
authors.initials: S
authors.lastname: Kitagawa
authors.forename: Neil R
authors.initials: NR
authors.lastname: Champness
authors.forename: Martin
authors.initials: M
authors.lastname: Schröder