Dipolar molecular rotors in the metal-organic framework crystal IRMOF-2

被引：108

作者：

Winston, Erick B. ^{[1
]}

Lowell, Peter J. ^{[1
]}

Vacek, Jaroslav ^{[2
,3
]}

Chocholousova, Jana ^{[2
,3
]}

Michl, Josef ^{[2
,3
]}

Price, John C. ^{[1
]}

机构：

[1] Univ Colorado, Dept Phys, Boulder, CO 80309 USA

[2] Univ Colorado, Dept Chem, Boulder, CO 80309 USA

[3] Acad Sci Czech Republ, Inst Organ Chem & Biochem, Prague, Czech Republic

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2008年 / 10卷 / 34期

关键词：

D O I：

10.1039/b808104b

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Rotating polar linker groups in the cubic metal-organic framework single crystal known as IRMOF-2 were investigated for freedom of motion, response to an external electric field, and effects of dipole-dipole interactions. The crystals consist of octahedrally coordinated zinc oxide clusters linked by the bromo-terephthalate group, which contains a rotatable bromo-p-phenylene moiety. We confirmed the rotation by dielectric spectroscopy and found a 7.3 kcal mol(-1) barrier. The non-polar analog, IRMOF-1, containing terephthalic acid, was used as a control system. DFT and MP2 computations of the rotational barrier yield results in agreement with the observation, with B3LYP/SDD being the best. A Monte Carlo analysis of the equilibrium polarization fluctuations was used to assess the possibility of polar ordering and the potential for electro-optic applications.

引用

页码：5188 / 5191

页数：4

共 35 条

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