1. Reversible Multiphase Transition in a BioMOF and Its Distinctive Luminescence Turn-On in Alcohol Vapor
- Author
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Weigang Lu, Mo Xie, Yong-Liang Huang, Dan Li, Dong Luo, Yifang Zhao, Yan Yan Li, and Jian-Ping Bai
- Subjects
Materials science ,Vapor pressure ,Stacking ,chemistry.chemical_element ,02 engineering and technology ,Zinc ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,01 natural sciences ,Porphyrin ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,Molecule ,General Materials Science ,Metal-organic framework ,Methanol ,0210 nano-technology ,Luminescence - Abstract
Solvothermal reaction of zinc meso-tetra(4-carboxyphenyl)porphyrin and 2,6-diaminopurine with zinc salt in DMF affords a three-dimensional bioMOF (1-α). Its infinite rod-shaped building block features an alternation of octahedral Zn4O and paddle-wheel Zn2 clusters bridged by 2,6-diaminopurines. The paddle-wheel Zn2 cluster undergoes reversible transformation with half into quasi-paddle-wheel Zn2 cluster and the other half into two tetrahedral mononuclear clusters upon release/uptake of guest molecules, resulting in a new phase 1-β. This single-crystal to single-crystal transformation is accompanied by luminescence on/off switching, possibly associated with the structural conversion between the porphyrin-ligand-based photoactive 1-α and the porphyrin-stacking-caused non-photoactive 1-β. Interestingly, 1-β exhibits quick luminescence turn-on in alcohol vapor instead of other volatile organic solvents by transforming into an intermediate phase 1-γ, which shows a partial luminescence enhancing likely due to the intermittent porphyrin π-π stacking. In view of experimental results and theoretical calculations, this distinctive alcohol-vapor-induced luminescence turn-on is attributed to the coordination ability to porphyrin-bound zinc ion, molecular size, and vapor pressure, in which methanol and ethanol are particularly favored.
- Published
- 2019