Citation: Bin XU, Shufeng ZHANG, Feifan LANG, Chunyan NI, Bing WU, Jianping LANG. Photoreactive pyrene-based Zn?? metal-organic frameworks: Solid-state [2+2] cycloaddition and tunable luminescence[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(10): 2119-2126. doi: 10.11862/CJIC.20260140 shu

Photoreactive pyrene-based Zn?? metal-organic frameworks: Solid-state [2+2] cycloaddition and tunable luminescence

Bin XU ¹ ,
Shufeng ZHANG ¹ ,
Feifan LANG ^1,, ,
Chunyan NI ¹ ,
Bing WU ^2,, ,
Jianping LANG ^1,,

1.
Suzhou Key Laboratory of Precision Transformation of Resource Molecules, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China
2.
Analysis and Testing Center, Soochow University, Suzhou, Jiangsu 215123, China

Corresponding author: Feifan LANG, fflangchem@suda.edu.cn Bing WU, wubing@suda.edu.cn Jianping LANG, jplang@suda.edu.cn
Received Date: 8 March 2026
Revised Date: 27 August 2026

Figures(4)

Solvothermal reactions of 2, 7-bis(4-pyridylvinyl)pyrene (2, 7-bpep) with Zn(Ⅱ) salt and terephthalic acid (H₂PTA) and pimelic acid (H₂GDA) afforded two photoreactive metal-organic frameworks (MOFs), {[Zn₂(2, 7-bpep)₂(PTA)₂]·2DMA}_n (MOF1) and [Zn(2, 7-bpep)(GDA)]_n (MOF2) (DMA=N, N-dimethylacetamide). Single-crystal X-ray diffraction analysis reveals that the 2, 7-bpep ligands adopt a face-to-face arrangement with olefinic double bonds positioned at distances consistent with Schmidt's criteria, thereby enabling solid-state [2+2] photocycloaddition. Upon irradiation with 420 nm visible light, both MOFs undergo quantitative [2+2] cycloaddition to yield the corresponding cyclobutane-linked frameworks (MOF1C and MOF2C), while MOF1C retains crystallinity. Photophysical studies show that these transformations cause pronounced blue shifts in emission relative to the parent frameworks, attributable to disrupted π-conjugation upon cyclobutane formation. These findings demonstrate that rational preorganization of photoactive ligands within MOFs provides an effective strategy for controlling solid-state photoreactivity and tuning luminescence properties, offering insights into the design of photoresponsive functional materials.
- metal-organic frameworks,
- pyrene ligand,
- [2+2] photocycloaddition,
- tunable fluorescence
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