Coordination-Driven Fluorescent J-Aggregates in a Perylenetetracarboxylate-Based MOF: Permanent Porosity and Proton Conductivity

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• 作者：Nivedita Sikdar ; Dipak Dutta ; Ritesh Haldar ; Turjya Ray ; Arpan Hazra ; Aninda Jiban Bhattacharyya ; Tapas Kumar Maji
• 刊名：Journal of Physical Chemistry C
• 出版年：2016
• 出版时间：June 30, 2016
• 年：2016
• 卷：120
• 期：25
• 页码：13622-13629
• 全文大小：512K
• 年卷期：0
• ISSN：1932-7455

文摘

Here we report the synthesis and structural characterizations of a new 3D functional metal–organic framework {[K₈(PTC)₂(H₂O)_1.5]·4H₂O}_n formed by the self-assembly of K^I and chromophoric linker perylenetetracarboxylate (PTC). The structure determination shows a 3D pillared-layer framework, where perylene cores are arranged in an unusual end-to-end off-slipped and zigzag arrangement directed by K^I–carboxylate bonding. Photophysical studies revealed a broad absorption band with λ_max of 531 nm and bathochromically shifted red emission centered at 655 nm. This characteristic emission has been assigned due to J-coupling of the PTC linkers in the solid state. The framework contains 1D water-filled channel, and the desolvated framework shows permanent porosity, “as realized by type-I CO₂ adsorption profile at 195 K. Interestingly, the guest and coordinated water molecules in the framework are connected via H-bonding and based on these characteristics, the framework was further exploited for proton conduction. It shows remarkable conductivity of 1 × 10^–3 S cm^–1 under ambient conditions (98% RH) with low activation energy.