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The impact of N,N′-ditopic ligand length and geometry on the structures of zinc-based mixed-linker metal–organic frameworks.
- Source :
- CrystEngComm; 10/7/2017, Vol. 19 Issue 37, p5549-5557, 9p
- Publication Year :
- 2017
-
Abstract
- Combining Zn(NO<subscript>3</subscript>)<subscript>2</subscript>·6H<subscript>2</subscript>O with a series of dicarboxylic acids in the presence of the N,N′-ditopic ligand di(4-pyridyl)-1H-pyrazole (Hdpp) results in a series of mixed-linker metal–organic frameworks (MOFs) that have been crystallographically characterised. The reaction with 1,4-benzenedicarboxylic acid (H<subscript>2</subscript>bdc) gives [Zn<subscript>2</subscript>(bdc)<subscript>2</subscript>(Hdpp)<subscript>2</subscript>]·2DMF 1, which shows Zn<subscript>2</subscript>(μ-carboxylate)<subscript>2</subscript>(carboxylate)<subscript>2</subscript> secondary building units (SBUs) linked by bdc ligands into sheets, and these are pillared by the Hdpp linkers into a doubly-interpenetrated three-dimensional network. The reaction with 1,4-naphthalene dicarboxylic acid (H<subscript>2</subscript>ndc-1,4) gives two products: [Zn<subscript>2</subscript>(1,4-ndc)<subscript>2</subscript>(Hdpp)]·4DMF 2a forms a three-dimensional network in which sheets, formed from Zn<subscript>2</subscript>(carboxylate)<subscript>4</subscript>‘paddle-wheel’ SBUs being linked by 1,4-ndc, are connected together by Hdpp pillars, whereas [Zn(1,4-ndc)(Hdpp)]·DMF 2b forms a fourfold interpenetrated structure based on diamondoid networks with single zinc centres as nodes. The reaction with 1,3-benzenedicarboxylic acid (H<subscript>2</subscript>mbdc) produces [Zn(mbdc)(Hdpp)]·DMF 3, which forms a two-dimensional network with (4,4) topology in which ZnO<subscript>2</subscript>N<subscript>2</subscript> nodes are interlinked by mbdc and Hdpp linkers. The reaction with 5-methyl-1,3-benzenedicarboxylic acid (H<subscript>2</subscript>mbdc-Me) also forms a two-dimensional network structure, [Zn<subscript>2</subscript>(mbdc-Me)<subscript>2</subscript>(Hdpp)<subscript>2</subscript>]·DMF 4, albeit wherein dicarboxylates bridge between zinc-dicarboxylate tapes, themselves formed by interlinking of Zn<subscript>2</subscript>(μ-carboxylate)<subscript>2</subscript>(carboxylate)<subscript>2</subscript> SBUs similar to those in 1. Finally, the reaction with 2,6-naphthalene dicarboxylic acid (H<subscript>2</subscript>ndc-2,6) yields two crystalline species, both having the formula [Zn<subscript>2</subscript>(2,6-ndc)<subscript>2</subscript>(Hdpp)]·DMF 5a/5b and possessing infinite zinc-carboxylate chain motifs interlinked by both naphthalene rings and Hdpp linkers into a three-dimensional framework. In compounds 1, 2b, 3 and 4, the pyrazole NH groups are involved in hydrogen bonding that serves to link either interpenetrated networks or neighbouring sheets together. However, in 2a and 5a/5b the NH groups project into the pores of the framework enabling interactions with guest molecules. [ABSTRACT FROM AUTHOR]
- Subjects :
- METAL-organic frameworks
LIGANDS (Chemistry)
NITROGEN
Subjects
Details
- Language :
- English
- ISSN :
- 14668033
- Volume :
- 19
- Issue :
- 37
- Database :
- Complementary Index
- Journal :
- CrystEngComm
- Publication Type :
- Academic Journal
- Accession number :
- 125341528
- Full Text :
- https://doi.org/10.1039/c7ce01447c