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

Danil N. Dybtsev, Maxim Yutkin, Denis G. Samsonenko, Vladimir P. Fedin, Alexey L. Nuzhdin, Andrey A. Bezrukov, Konstantin P. Bryliakov, Evgeniy P. Talsi, Rodion V. Belosludov, Hiroshi Mizuseki, Yoshiyuki Kawazoe, Oleg S. Subbotin, Vladimir R. Belosludov

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61 Scopus citations

Abstract

Two new, homochiral, porous metal-organic coordination polymers [Zn 2(ndc){(R)-man)(dmf)]·3DMF and [Zn2(bpdc){(R)-man} (dmf)]·2DMF (ndc = 2,6-naphthalenedicarboxylate ; bpdc=4,4′- biphenyldicarboxylate ; man = mandelate; dmf=N,N'-dimethylformamide) have been synthesized by heating ZnIInitrate, H2ndc or H 2bpdc and chiral (R)-mandelic acid (H2man) 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 [Zn2(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 [Zn2(bdc)((S)-lac}(dmf)]·DMF, while the latter demonstrates decent enantioselectivity toward precursor of chiral anticancer drug sulforaphane, CH3SO(CH2)4OH. The new homochiral porous metal-organic coordination polymers are capable of catalyzing a highly selective oxidation of bulkier sulfides (2-NaphSMe (2-C10H 7SMe) and PhSCH2Ph) that could not be achieved by the smaller-pore [Zn2(bdc)((S)-lac}(dmf)]·DMF. The sorption of different guest molecules (both R and S isomers) into the chiral pores of [Zn2(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)PhSOCH3 sulfinyl group.

Original languageEnglish (US)
Pages (from-to)10348-10356
Number of pages9
JournalChemistry - A European Journal
Volume16
Issue number34
DOIs
StatePublished - Sep 10 2010

Keywords

  • Chirality
  • Density functional calculations
  • Metal-organic frameworks
  • Porous materials

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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