Citation: Tong TAO, Shufeng ZHANG, Feifan LANG, Chunyan NI, Bing WU, Jianping LANG. Synthesis, structures, and daylight-induced [2+2] cycloaddition reactivity of two Cd(Ⅱ)-based pillared-layer coordination polymers[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(6): 1121-1130. doi: 10.11862/CJIC.20260115 shu

Synthesis, structures, and daylight-induced [2+2] cycloaddition reactivity of two Cd(Ⅱ)-based pillared-layer coordination polymers

Tong TAO 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: 6 April 2026
Revised Date: 2 May 2026

Figures(4)

Two novel Cd(Ⅱ)-based pillared-layer coordination polymers, [Cd₂(1,5-bpvn)₂(bdc)₂]_n (CP1) and [Cd(1,5-bpvn)(4,4′-bpdc)]_n (CP2), were constructed via a solvothermal strategy using the bis-olefin ligand 1,5-bis[(E)-2-(pyridin-4-yl)vinyl]naphthalene (1,5-bpvn) in combination with auxiliary dicarboxylate ligands of different axial lengths, namely terephthalic acid (H₂bdc) and biphenyl-4,4′-dicarboxylic acid (4,4′-H₂bpdc). Single-crystal X-ray diffraction analyses reveal that the axial length of the auxiliary ligands plays a crucial role in regulating the framework topology and interpenetration mode. CP1 exhibits a typical two-fold interpenetrated framework with pcu topology, whereas CP2 adopts a rare self-penetrating architecture with the Schläfli symbol {4⁴·6¹⁰·8}. In CP1, the 1,5-bpvn ligands display both in-phase and out-of-phase packing arrangements, with the distance and orientation between adjacent olefin groups satisfying the geometric criteria for a solid-state [2+2] photocycloaddition reaction. Upon exposure to daylight, CP1 underwent a single-crystal-to-single-crystal transformation, affording the photoproduct [Cd₂(tpdnpp)(bdc)₂]_n (CP1-C), which contains the bis(cyclobutane) dimer tetrakis(pyridin-4-yl)-1,2,11,12-diethano[2.2]naphthalenophane (tpdnpp). In contrast, the 1,5-bpvn ligands in CP2 adopt significantly twisted conformations, resulting in larger C=C separations that are unfavorable for photocycloaddition. In addition, the luminescent properties of CP1 before and after the photocycloaddition reaction were investigated, revealing the influence of the photochemical transformation on the emission behavior.
- pillar-layered coordination polymer,
- self-penetrated framework,
- daylight,
- [2+2] photocycloaddition,
- single-crystal-to-single-crystal transformation
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