Modular, Homochiral, Porous Coordination Polymers: Rational Design, Enantioselective Guest Exchange Sorption and Ab Initio Calculations of Host–Guest Interactions
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Chemistry - A European Journal
ISSN: 0947-6539
, E-ISSN: 1521-3765
|
| Вых. Данные |
Год: 2010,
Том: 16,
Номер: 34,
Страницы: 10348-10356
Страниц
: 9
DOI:
10.1002/chem.201000522
|
| Ключевые слова |
Chirality, Density functional calculations, Metal-organic frameworks, Porous materials |
| Авторы |
Dybtsev Danil N.
1,2
,
Yutkin Maxim P.
1
,
Samsonenko Denis G.
1
,
Fedin Vladimir P.
1
,
Nuzhdin Alexey L.
3
,
Bezrukov Andrey A.
3
,
Bryliakov Konstantin P.
3
,
Talzi Evgeniy P.
3
,
Belosludov Rodion V.
4
,
Mizuseki Hiroshi
4
,
Kawazoe Yoshiyuki
4
,
Subbotin Oleg S.
1
,
Belosludov Vladimir R.
1
|
| Организации |
| 1 |
Институт неорганической химии им. А.В. Николаева СО РАН
|
| 2 |
Pohang University of Science and Technology
|
| 3 |
Институт катализа им. Г.К. Борескова СО РАН
|
| 4 |
Tohoku University
|
|
Информация о финансировании (4)
|
1
|
Российский фонд фундаментальных исследований
|
08-03-12007
|
|
2
|
Российский фонд фундаментальных исследований
|
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
|
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.