Reversible Interconversion between Luminescent Isomeric Metal–Organic Frameworks of [Cu<sub>4</sub>I<sub>4</sub>(DABCO)<sub>2</sub>] (DABCO=1,4‐Diazabicyclo[2.2.2]octane)
書誌事項
- 公開日
- 2010-01-26
- 権利情報
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- http://onlinelibrary.wiley.com/termsAndConditions#vor
- DOI
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- 10.1002/chem.200900743
- 公開者
- Wiley
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説明
<jats:title>Abstract</jats:title><jats:p>The metal–organic frameworks (MOF) of cluster [Cu<jats:sub>4</jats:sub>I<jats:sub>4</jats:sub>(DABCO)<jats:sub>2</jats:sub>] (DABCO=1,4‐diazabicyclo[2.2.2]octane) have been prepared and characterized as two different crystalline forms, <jats:bold>I</jats:bold> and <jats:bold>II</jats:bold>. Form <jats:bold>I</jats:bold> is obtained by reaction of DABCO and CuI in aqueous solution or by solvothermal reaction, while form <jats:bold>II</jats:bold> is obtained by reacting DABCO and CuI in acetonitrile. Their luminescence properties in the solid state have been analyzed at room temperature and at 77 K. MOF <jats:bold>II</jats:bold> has bright emission with a maximum at 556 nm that shifts bathochromically at low temperature in conjunction with a marked change in the colour of the emission. The emission of MOF <jats:bold>I</jats:bold> has a maximum at 580 nm and a less pronounced temperature dependence. The peculiar luminescence properties of the two isomers have been interpreted by utilising current knowledge on the excited states properties of Cu<jats:sup>I</jats:sup> cubane clusters. The two isomers exhibit a high degree of porosity and can release the disordered solvent molecules trapped in the channels, whilst preserving the crystal structure. Isomer <jats:bold>I</jats:bold> can be converted into <jats:bold>II</jats:bold> on exposure to acetonitrile or methanol vapour, whereas <jats:bold>II</jats:bold> reverts to <jats:bold>I</jats:bold> when heated in a closed pan at 250 °C.</jats:p>
収録刊行物
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- Chemistry – A European Journal
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Chemistry – A European Journal 16 (5), 1553-1559, 2010-01-26
Wiley