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Modular, homochiral, porous coordination polymers: Rational design, enantioselective guest exchange sorption and ab initio calculations of host-guest interactions

Chemistry - A European Journal, ISSN: 0947-6539, Vol: 16, Issue: 34, Page: 10348-10356
2010
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Article Description

Two new, homochiral, porous metal-organic coordination polymers [Zn (ndc){(R)-man)(dmf)]·3DMF and [Zn(bpdc){(R)-man} (dmf)]·2DMF (ndc = 2,6-naphthalenedicarboxylate ; bpdc=4,4′- biphenyldicarboxylate ; man = mandelate; dmf=N,N'-dimethylformamide) have been synthesized by heating Znnitrate, Hndc or H bpdc and chiral (R)-mandelic acid (Hman) 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(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(bdc)((S)-lac}(dmf)]·DMF, while the latter demonstrates decent enantioselectivity toward precursor of chiral anticancer drug sulforaphane, CHSO(CH)OH. The new homochiral porous metal-organic coordination polymers are capable of catalyzing a highly selective oxidation of bulkier sulfides (2-NaphSMe (2-CH SMe) and PhSCHPh) that could not be achieved by the smaller-pore [Zn(bdc)((S)-lac}(dmf)]·DMF. The sorption of different guest molecules (both R and S isomers) into the chiral pores of [Zn(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 C-H⋯O bond between the DMF methyl group and the (S)PhSOCH sulfinyl group. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bibliographic Details

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

Wiley

Chemical Engineering; Chemistry

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