期刊
JOURNAL OF MATERIALS CHEMISTRY C
卷 9, 期 16, 页码 5544-5553出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1tc00398d
关键词
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资金
- Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) [PGC2018102052-A-C22, PGC2018-102052-B-C21, PGC2018-099296-BI00]
- Junta de Andaluci'nce, Innovation and Universities (MCIU/AEI/FEDER, UE) [FQM-394]
- Gobierno Vasco/Eusko Jaurlaritza [IT1005-16]
- University of the Basque Country (UPV/EHU) [GIU 17/13]
- Ministerio de Ciencia, Innovacio'n y Universidades the FPU contract
- European funding (ERDF)
- European funding (ESF)
This work reports the synthesis and characterization of enantiomeric pair of 3D coordination polymers based on heavy alkaline-earth metal ions and cyclic aliphatic chiral linkers. These materials exhibit dense framework and intriguing photophysical properties, including intense fluorescence and long-lasting phosphorescence, as well as circularly polarized luminescence in accordance with their chiral nature.
This work reports on the synthesis and characterization of an enantiomeric pair of 3D coordination polymers (CPs) based on heavy alkaline-earth metal ions and cyclic aliphatic chiral linkers, i.e. [Ba-2(mu-L-pyro)(2)(mu(4)-NO3)(mu(3)-form)](n) (1-L) and [Ba-2(mu-L-pyro)(2)(mu(4)-NO3)(mu(3)-form)](n) (1-D) [where pyro = pyroglutamate and form = formate]. These materials present a dense framework built up from the junction of barium(ii) ions by means of three bridging ligands showing different connectivity, which affords robustness and, in turn, large stability to the crystal building. l- or d-pyro ligands are formed in situ during the solvothermal synthesis through the cyclization of the corresponding chiral glutamine species, which does not affect the chirality of the resulting ligand such that the structures preserve an enantiopure nature. A deep study of the photophysical properties reveals that these CPs display intriguing photoluminescence (PL) properties involving intense fluorescence and long-lasting phosphorescence, even at room temperature, which have been deeply characterized by diffuse reflectance, variable-temperature emission analysis and time-resolved emission spectra (TRES). The experimental results are sustained by DFT calculations that decipher the PL mechanism. Moreover, these materials exhibit intense pyro-based circularly polarized luminescence in agreement with their chiral nature, which constitutes the first example of an AE-based CP able to display CPL signals.
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