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Modular, Homochiral, Porous Coordination Polymers: Rational Design, Enantioselective Guest Exchange Sorption and Ab Initio Calculations of Host–Guest Interactions
Author(s) -
Dybtsev Danil N.,
Yutkin Maxim P.,
Samsonenko Denis G.,
Fedin Vladimir P.,
Nuzhdin Alexey L.,
Bezrukov Andrey A.,
Bryliakov Konstantin P.,
Talsi Evgeniy P.,
Belosludov Rodion V.,
Mizuseki Hiroshi,
Kawazoe Yoshiyuki,
Subbotin Oleg S.,
Belosludov Vladimir R.
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201000522
Subject(s) - metal organic framework , chemistry , sorption , molecule , ab initio , polymer chemistry , crystallography , organic chemistry , adsorption
Two new, homochiral, porous metal–organic coordination polymers [Zn 2 (ndc){( R )‐man}(dmf)]⋅3DMF and [Zn 2 (bpdc){( R )‐man}(dmf)]⋅2DMF (ndc=2,6‐naphthalenedicarboxylate; bpdc=4,4′‐biphenyldicarboxylate; man=mandelate; dmf= N , N ′‐dimethylformamide) have been synthesized by heating Zn II nitrate, H 2 ndc or H 2 bpdc and chiral ( R )‐mandelic acid (H 2 man) in DMF. The colorless crystals were obtained and their structures were established by single‐crystal X‐ray diffraction. These isoreticular structures share the same topological features as the previously reported zinc(II) terephthalate lactate [Zn 2 (bdc){( S )‐lac}(dmf)]⋅DMF framework, but have larger pores and opposite absolute configuration of the chiral centers. The enhanced pores size results in differing stereoselective sorption properties: the new metal–organic frameworks effectively and stereoselectively ( ee up to 62 %) accommodate bulkier guest molecules (alkyl aryl sulfoxides) than the parent [Zn 2 (bdc){( S )‐lac}(dmf)]⋅DMF, while the latter demonstrates decent enantioselectivity toward precursor of chiral anticancer drug sulforaphane, CH 3 SO(CH 2 ) 4 OH. The new homochiral porous metal–organic coordination polymers are capable of catalyzing a highly selective oxidation of bulkier sulfides (2‐NaphSMe (2‐C 10 H 7 SMe) and PhSCH 2 Ph) that could not be achieved by the smaller‐pore [Zn 2 (bdc){( S )‐lac}(dmf)]⋅DMF. The sorption of different guest molecules (both R and S isomers) into the chiral pores of [Zn 2 (bdc){( S )‐lac}(dmf)]⋅DMF was modeled by using ab initio calculations that provided a qualitative explanation for the observed sorption enantioselectivity. The high stereo‐preference is accounted for by the presence of coordinated inner‐pore DMF molecule that forms a weak CH⋅⋅⋅O bond between the DMF methyl group and the ( S )‐PhSOCH 3 sulfinyl group.