Modular, Homochiral, Porous Coordination Polymers: Rational Design, Enantioselective Guest Exchange Sorption and Ab Initio Calculations of Host–Guest Interactions Full article
| Journal |
Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765 |
||||||||
|---|---|---|---|---|---|---|---|---|---|
| Output data | Year: 2010, Volume: 16, Number: 34, Pages: 10348-10356 Pages count : 9 DOI: 10.1002/chem.201000522 | ||||||||
| Tags | Chirality, Density functional calculations, Metal-organic frameworks, Porous materials | ||||||||
| Authors |
|
||||||||
| Affiliations |
|
Funding (4)
| 1 | Russian Foundation for Basic Research | 08-03-12007 |
| 2 | Russian Foundation for Basic Research | 09-03-90414 |
| 3 | Ministry of Science ICT and Future Planning | R31-2008-000-10059-0 |
| 4 | Ministry of Education, Culture, Sports, Science and Technology | 19651039 |
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.
Cite:
Dybtsev D.N.
, Yutkin M.P.
, Samsonenko D.G.
, Fedin V.P.
, Nuzhdin A.L.
, Bezrukov A.A.
, Bryliakov K.P.
, Talzi E.P.
, Belosludov R.V.
, Mizuseki H.
, Kawazoe Y.
, Subbotin O.S.
, Belosludov V.R.
Modular, Homochiral, Porous Coordination Polymers: Rational Design, Enantioselective Guest Exchange Sorption and Ab Initio Calculations of Host–Guest Interactions
Chemistry - A European Journal. 2010. V.16. N34. P.10348-10356. DOI: 10.1002/chem.201000522 WOS Scopus РИНЦ ANCAN OpenAlex
Modular, Homochiral, Porous Coordination Polymers: Rational Design, Enantioselective Guest Exchange Sorption and Ab Initio Calculations of Host–Guest Interactions
Chemistry - A European Journal. 2010. V.16. N34. P.10348-10356. DOI: 10.1002/chem.201000522 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Feb 28, 2010 |
| Accepted: | Jun 28, 2010 |
| Published online: | Aug 20, 2010 |
| Published print: | Sep 10, 2010 |
Identifiers:
| Web of science: | WOS:000282539700013 |
| Scopus: | 2-s2.0-77956449803 |
| Elibrary: | 15331356 |
| Chemical Abstracts: | 2010:1154357 |
| Chemical Abstracts (print): | 153:609061 |
| OpenAlex: | W2134210496 |