Issue 30, 2014

Synthesis, characterization and properties of a family of lead(ii)–organic frameworks based on a multi-functional ligand 2-amino-4-sulfobenzoic acid exhibiting auxiliary ligand-dependent dehydration–rehydration behaviours

Abstract

A systematic investigation is reported of the use of the multi-functional ligand 2-amino-4-sulfobenzoate (asba2−) to construct lead(II)–organic frameworks in the presence and absence of N-donor auxiliary ligands phen, bipy and bix [phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine and bix = 1,4-(methylene-benzene)bisimidazole]. Under ambient, aqueous conditions the assembly of asba2− with Pb(II) and phen or bipy leads to two iso-structural 2D double-layer frameworks, {[Pb2(asba)2(phen)2(H2O)]·2H2O}n (1) and {[Pb2(asba)2(bipy)2(H2O)]·2H2O}n (2). [Pb2(asba)2(bix)2(H2O)2]n (3) is obtained in the presence of the auxiliary ligand bix and possesses a 3D network built up from 2D Pb(II)-asba2−-bridged double-layer pillared by bix. A 2D (4,4) topological network [Pb(asba)(H2O)]n (4) is obtained in the absence of any second ligand or presence of some bistriazole bridging spacers. The coordination modes of the ligand asba2− in 1–4 are greatly dependent on the type of auxiliary ligand and the compounds exhibit auxiliary ligand-dependent dehydration–rehydration behaviours; 1 shows in situ rapid and reversible dehydration–rehydration behaviour in air, while the iso-structural compound 2 loses crystallinity in air and transforms into {[Pb2(asba)2(bipy)2(H2O)]·H2O}n (2A) verified by TGA, elemental analysis and powder X-ray diffraction analysis (PXRD). 3 also shows reversible dehydration–rehydration behaviour, but it takes around one week to rehydrate even after exposure to water vapor, while the dehydrated phase of 4 rehydrates to a new crystalline material. 1 and 3 fall within the category of the “recoverable collapsing” and “guest-induced re-formation” frameworks. The water molecules in 1 and 3 have some influence on their solid state fluorescent emission intensity.

Graphical abstract: Synthesis, characterization and properties of a family of lead(ii)–organic frameworks based on a multi-functional ligand 2-amino-4-sulfobenzoic acid exhibiting auxiliary ligand-dependent dehydration–rehydration behaviours

Supplementary files

Article information

Article type
Paper
Submitted
05 Mar 2014
Accepted
24 May 2014
First published
28 May 2014

Dalton Trans., 2014,43, 11597-11610

Author version available

Synthesis, characterization and properties of a family of lead(II)–organic frameworks based on a multi-functional ligand 2-amino-4-sulfobenzoic acid exhibiting auxiliary ligand-dependent dehydration–rehydration behaviours

K. Zhang, Z. Zhong, L. Zhang, C. Jing, L. M. Daniels and R. I. Walton, Dalton Trans., 2014, 43, 11597 DOI: 10.1039/C4DT00659C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements