Structure and Characterization of a Novel 3D Lead Phosphonate Metal–Organic Framework with Cationic Layer Based on Weak Pb–O(N) Contact

Kui-Rong Ma; Dao-Jun Zhang; Yu-Lan Zhu

doi:10.1071/CH09382

RESEARCH ARTICLE

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Structure and Characterization of a Novel 3D Lead Phosphonate Metal–Organic Framework with Cationic Layer Based on Weak Pb–O(N) Contact

Kui-Rong Ma ^A ^C , Dao-Jun Zhang ^B and Yu-Lan Zhu ^A

+ Author Affiliations

- Author Affiliations

^A Jiangsu Key Laboratory for Chemistry of Low-dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, 223300 Huai’an, China.

^B State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 130021 Changchun, China.

^C Corresponding author. Email: mlkr0477@sina.com

Australian Journal of Chemistry 63(3) 452-457 https://doi.org/10.1071/CH09382
Submitted: 13 July 2009 Accepted: 3 September 2009 Published: 26 March 2010

Abstract

A novel lead-phosphonate, [Pb₂(HL)]·(NO₃)·2(H₂O) 1 (H₄L = H₂O₃PCH₂N(C₄H₈)NCH₂PO₃H₂ N,N′-piperazinebis(methylenephosphonic acid), so HL = O₃PCH₂NH(C₄H₈)NCH₂PO₃), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG-DTA, and X-ray single-crystal diffraction. Compound 1 possesses a 2D cationic layer structure built from inorganic chains with three types of eight-membered rings arranged in an ABAC manner. In 1, both crystallographic distinct Pb(II) ions adopt three-coordination geometry, and a counter anion NO₃ ^– and two lattice water molecules occupy the voids between 2D layers. After the removal of solvent, the size of tunnel formed by 2D layers is 137.9 Å³ per unit cell, comprising 17.0% of the crystal volume based on the crystal structure. When the bond length of Pb–O(N) extended to 3.10 Å, a 3D metal–organic framework was constructed via long Pb–O(N) contacts, simultaneously accompanied by the hemi- to holo-directed transition in coordination geometry of Pb(II). Except for the long Pb–O contacts, a 3D supramolecular network is also formed by hydrogen bonds (N–H···O, O–H···O, and C–H···O), van der Waals forces as well as electrostatic interactions. The result of fluorescence measurements indicates that 1 shows a fluorescent emission band at 465 nm (λ_excitation = 215 nm).

Acknowledgements

The authors are grateful to the financial support from The National Natural Science Foundation of China and Open Fund of Jiangsu Key Laboratory for Chemistry of Low-dimensional Materials (Projects Nos. 20671038 and JSKC09068).

References

Structure and Characterization of a Novel 3D Lead Phosphonate Metal–Organic Framework with Cationic Layer Based on Weak Pb–O(N) Contact

Abstract

Acknowledgements

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