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The crystalline sponge method: MOF terminal ligand effects.

Ramadhar TR, Zheng SL, Chen YS, Clardy J - Chem. Commun. (Camb.) (2015)

Bottom Line: Bromide and chloride analogs of the commonly used zinc iodide-based metal organic framework for the crystalline sponge method were synthesized and evaluated.Inclusion of (1R)-(-)-menthyl acetate into these MOFs was analysed using third-generation synchrotron radiation, and the effects and potential benefits of varying the MOF terminal ligand are discussed.

View Article: PubMed Central - PubMed

Affiliation: Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, 240 Longwood Avenue, Boston, Massachusetts 02115, USA. jon_clardy@hms.harvard.edu.

ABSTRACT
Bromide and chloride analogs of the commonly used zinc iodide-based metal organic framework for the crystalline sponge method were synthesized and evaluated. Inclusion of (1R)-(-)-menthyl acetate into these MOFs was analysed using third-generation synchrotron radiation, and the effects and potential benefits of varying the MOF terminal ligand are discussed.

No MeSH data available.


Crystalline sponges with various terminal halide ligands and the (1R)-(–)-menthyl acetate guest employed in the current study.
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fig1: Crystalline sponges with various terminal halide ligands and the (1R)-(–)-menthyl acetate guest employed in the current study.

Mentions: The applicability of single crystal X-ray diffraction (SC-XRD) for structural analysis is limited by its requirement of a single crystal of the material to be analysed. Fujita and co-workers have recently described a method that could bypass this requirement by using a crystal of a metal organic framework (MOF) to orient host molecules within its pores. Their approach is called the crystalline sponge method,1 and the most widely used MOF sponge is {[(ZnI2)3(tris(4-pyridyl)-1,3,5-triazene)2]·x(solvent)}n (1a) (Fig. 1).2 In addition to providing a crystalline host for difficult-to-crystallize guests, this sponge’s heavy atoms allow for the absolute stereochemical determination of chiral guests with only light atoms through anomalous dispersion using Mo Kα radiation. The original report was met with enthusiasm3 and subsequent studies illustrated its utility,4 but the approach’s crystallographic quality, as highlighted by the incorrect stereochemical determination of miyakosyne A,5 has also been criticized.6 We previously reported an improved MOF synthetic procedure and the establishment of crystallographic guidelines that were derived from probing the systems with high-flux synchrotron radiation.7


The crystalline sponge method: MOF terminal ligand effects.

Ramadhar TR, Zheng SL, Chen YS, Clardy J - Chem. Commun. (Camb.) (2015)

Crystalline sponges with various terminal halide ligands and the (1R)-(–)-menthyl acetate guest employed in the current study.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4490044&req=5

fig1: Crystalline sponges with various terminal halide ligands and the (1R)-(–)-menthyl acetate guest employed in the current study.
Mentions: The applicability of single crystal X-ray diffraction (SC-XRD) for structural analysis is limited by its requirement of a single crystal of the material to be analysed. Fujita and co-workers have recently described a method that could bypass this requirement by using a crystal of a metal organic framework (MOF) to orient host molecules within its pores. Their approach is called the crystalline sponge method,1 and the most widely used MOF sponge is {[(ZnI2)3(tris(4-pyridyl)-1,3,5-triazene)2]·x(solvent)}n (1a) (Fig. 1).2 In addition to providing a crystalline host for difficult-to-crystallize guests, this sponge’s heavy atoms allow for the absolute stereochemical determination of chiral guests with only light atoms through anomalous dispersion using Mo Kα radiation. The original report was met with enthusiasm3 and subsequent studies illustrated its utility,4 but the approach’s crystallographic quality, as highlighted by the incorrect stereochemical determination of miyakosyne A,5 has also been criticized.6 We previously reported an improved MOF synthetic procedure and the establishment of crystallographic guidelines that were derived from probing the systems with high-flux synchrotron radiation.7

Bottom Line: Bromide and chloride analogs of the commonly used zinc iodide-based metal organic framework for the crystalline sponge method were synthesized and evaluated.Inclusion of (1R)-(-)-menthyl acetate into these MOFs was analysed using third-generation synchrotron radiation, and the effects and potential benefits of varying the MOF terminal ligand are discussed.

View Article: PubMed Central - PubMed

Affiliation: Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, 240 Longwood Avenue, Boston, Massachusetts 02115, USA. jon_clardy@hms.harvard.edu.

ABSTRACT
Bromide and chloride analogs of the commonly used zinc iodide-based metal organic framework for the crystalline sponge method were synthesized and evaluated. Inclusion of (1R)-(-)-menthyl acetate into these MOFs was analysed using third-generation synchrotron radiation, and the effects and potential benefits of varying the MOF terminal ligand are discussed.

No MeSH data available.