title: Modular, homochiral, porous coordination polymers: rational design, enantioselective guest exchange sorption and ab initio calculations of host-guest interactions.
abstract: 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 C-H...O bond between the DMF methyl group and the (S)-PhSOCH(3) sulfinyl group.
authors: Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Lavrentieva 3, 630090 Novosibirsk, Russian Federation.
authors: Danil N
authors: DN
authors: Dybtsev
authors: Maxim P
authors: MP
authors: Yutkin
authors: Denis G
authors: DG
authors: Samsonenko
authors: Vladimir P
authors: VP
authors: Fedin
authors: Alexey L
authors: AL
authors: Nuzhdin
authors: Andrey A
authors: AA
authors: Bezrukov
authors: Konstantin P
authors: KP
authors: Bryliakov
authors: Evgeniy P
authors: EP
authors: Talsi
authors: Rodion V
authors: RV
authors: Belosludov
authors: Hiroshi
authors: H
authors: Mizuseki
authors: Yoshiyuki
authors: Y
authors: Kawazoe
authors: Oleg S
authors: OS
authors: Subbotin
authors: Vladimir R
authors: VR
authors: Belosludov
mesh_terms: D004126:Dimethylformamide / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism; D014961:X-Ray Diffraction; D015032:Zinc / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D011108:Polymers; D004126:Dimethylformamide; D015032:Zinc