Citation: Yan XU, Suzhi LI, Yan LI, Lushun FENG, Wentao SUN, Xinxing LI. Structure variation of cadmium naphthalene-diphosphonates with the changing rigidity of N-donor auxiliary ligands[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(2): 395-406. doi: 10.11862/CJIC.20240226 shu

Structure variation of cadmium naphthalene-diphosphonates with the changing rigidity of N-donor auxiliary ligands

Department of Chemistry, School of Biological and Materials Engineering, Suqian University, Suqian, Jiangsu 223800, China

Corresponding author: Yan XU, 17101@squ.edu.cn Suzhi LI, lisuzhi2005@sina.com
Received Date: 17 June 2024
Revised Date: 5 September 2024

Figures(9)

Five cadmium naphthalene-diphosphonates, formulated as [Cd_1.5(1,4-ndpaH₂)₂(4,4′-bpyH)(4,4′-bpy)_0.5(H₂O)₂]₂ (1), [Cd(1,4-ndpaH₂)(1,4-bib)_0.5(H₂O)] (2), [Cd(1,4-ndpaH₃)₂(1,2-dpe)(H₂O)]·(1,2-dpe)·7H₂O (3), (1,2-bixH)[Cd₃(1,4-ndpaH)(1,4-ndpaH₂)₂(H₂O)₂] (4), and [Cd(1,4-ndpaH₂)(H₂O)]·H₂O (5), have been synthesized from the self-assembly reactions of 1,4-naphthalenediphosphonic acid (1,4-ndpaH₄) with Cd(NO₃)₂·4H₂O by introducing auxiliary ligands with variation of rigidity, such as 4,4′-bipyridine (4,4′-bpy), 1,4-bis(1-imidazolyl)benzene (1,4-bib), 1,2-di(4-pyridyl)ethylene (1,2-dpe), 1,3-di(4-pyridyl)propane (1,3-dpp), and bis(imidazol-1-ylmethyl)benzene (1,2-bix), respectively. Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework, in which the {Cd₃(PO₂)₂} trimers made up of corner-sharing two {CdO₄N₂} and one {CdO₆} octahedra are connected by phosphonate groups, forming a ribbon, which are cross-linked by 4,4′-bipy ligands, forming a 2D layer. Compound 2 shows a 3D open-framework structure, where chains of corner-sharing {CdO₄N} trigonal bipyramids and {PO₃C} tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups. A 1D ladder-like chain structure is found in compound 3, where the ladder-like chains made up of corner-sharing {CdO₅N} octahedra and {PO₃C} tetrahedra are connected by 1,4-ndpaH₂^2-. Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure, which is formed by ligand crosslinking double metal chains. Interestingly, In 4, flexible 1,2-bix was singly protonated, as guest molecules, filled between layer and layer, while flexible ligand 1,3-dpp is absent in 5. Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.
- naphthalene diphosphate,
- N-donor auxiliary ligands,
- crystal structure,
- rigidity,
- flexibility
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