A homochiral metal-organic framework with amino-functionalized pores

Issue title: Exploring the Relationships Between Main Group and f-Element Chemistry

Article type: Research Article

Authors: Rood, Jeffrey A. | Noll, Bruce C. | Henderson, Kenneth W.

Affiliations: Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-5670, USA

Note: [] Corresponding author. Email: khenders@nd.edu

Abstract: A new metal-organic framework [Zn2(Cam)2(apyr) ⊃ 2DMF], 4 (apyr = 2-aminopyrazine) has been synthesized by the high temperature equimolar reactions of zinc nitrate with the (+)-camphoric acid (H2Cam) in neat DMF solution. The crystal structure of 4 was determined by X-ray analyses and found to be a porous cubic network composed of linked zinc camphorate “paddlewheel” secondary building units and apyr pillars. The apyr pillars give amino-functionality to the pores. The extended structure of 4 contains guest DMF molecules trapped within the channels. Compound 4 is potentially porous and thermogravimetric analysis is consistent with the initial loss of guest DMF between 75 and 190°C, with the decomposition of the material at 430°C. The material was found to take up racemic alcohols into its pores, however no enantioselectivity was achieved. Reactivity studies of 4 with acetaldehyde show that the amino groups in the pores can be transformed into imine functionalities via post-synthetic covalent modification.

Keywords: zinc, metal-organic frameworks, homochiral, post-synthetic covalent modification

DOI: 10.1080/10241220903125989

Journal: Main Group Chemistry, vol. 8, no. 4, pp. 237-250, 2009