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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

Journal Article


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Abstract


  • Combining Zn(NO 3 ) 2 ·6H 2 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 2 bdc) gives [Zn 2 (bdc) 2 (Hdpp) 2 ]·2DMF 1, which shows Zn 2 (μ-carboxylate) 2 (carboxylate) 2 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 2 ndc-1,4) gives two products: [Zn 2 (1,4-ndc) 2 (Hdpp)]·4DMF 2a forms a three-dimensional network in which sheets, formed from Zn 2 (carboxylate) 4 '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 2 mbdc) produces [Zn(mbdc)(Hdpp)]·DMF 3, which forms a two-dimensional network with (4,4) topology in which ZnO 2 N 2 nodes are interlinked by mbdc and Hdpp linkers. The reaction with 5-methyl-1,3-benzenedicarboxylic acid (H 2 mbdc-Me) also forms a two-dimensional network structure, [Zn 2 (mbdc-Me) 2 (Hdpp) 2 ]·DMF 4, albeit wherein dicarboxylates bridge between zinc-dicarboxylate tapes, themselves formed by interlinking of Zn 2 (μ-carboxylate) 2 (carboxylate) 2 SBUs similar to those in 1. Finally, the reaction with 2,6-naphthalene dicarboxylic acid (H 2 ndc-2,6) yields two crystalline species, both having the formula [Zn 2 (2,6-ndc) 2 (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.

UOW Authors


  •   Burrows, Andrew D. (external author)
  •   Chan, Siobhan (external author)
  •   Gee, William (external author)
  •   Mahon, Mary F. (external author)
  •   Richardson, Christopher
  •   Sebestyen, Viorica (external author)
  •   Turski, Domenyk (external author)
  •   Warren, Mark (external author)

Publication Date


  • 2017

Citation


  • Burrows, A. D., Chan, S., Gee, W. J., Mahon, M. F., Richardson, C., Sebestyen, V. M., Turski, D. & Warren, M. R. (2017). The impact of N, N′-ditopic ligand length and geometry on the structures of zinc-based mixed-linker metal-organic frameworks. CrystEngComm, 19 (37), 5549-5557.

Scopus Eid


  • 2-s2.0-85029952777

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=6035&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/4985

Number Of Pages


  • 8

Start Page


  • 5549

End Page


  • 5557

Volume


  • 19

Issue


  • 37

Place Of Publication


  • United Kingdom

Abstract


  • Combining Zn(NO 3 ) 2 ·6H 2 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 2 bdc) gives [Zn 2 (bdc) 2 (Hdpp) 2 ]·2DMF 1, which shows Zn 2 (μ-carboxylate) 2 (carboxylate) 2 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 2 ndc-1,4) gives two products: [Zn 2 (1,4-ndc) 2 (Hdpp)]·4DMF 2a forms a three-dimensional network in which sheets, formed from Zn 2 (carboxylate) 4 '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 2 mbdc) produces [Zn(mbdc)(Hdpp)]·DMF 3, which forms a two-dimensional network with (4,4) topology in which ZnO 2 N 2 nodes are interlinked by mbdc and Hdpp linkers. The reaction with 5-methyl-1,3-benzenedicarboxylic acid (H 2 mbdc-Me) also forms a two-dimensional network structure, [Zn 2 (mbdc-Me) 2 (Hdpp) 2 ]·DMF 4, albeit wherein dicarboxylates bridge between zinc-dicarboxylate tapes, themselves formed by interlinking of Zn 2 (μ-carboxylate) 2 (carboxylate) 2 SBUs similar to those in 1. Finally, the reaction with 2,6-naphthalene dicarboxylic acid (H 2 ndc-2,6) yields two crystalline species, both having the formula [Zn 2 (2,6-ndc) 2 (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.

UOW Authors


  •   Burrows, Andrew D. (external author)
  •   Chan, Siobhan (external author)
  •   Gee, William (external author)
  •   Mahon, Mary F. (external author)
  •   Richardson, Christopher
  •   Sebestyen, Viorica (external author)
  •   Turski, Domenyk (external author)
  •   Warren, Mark (external author)

Publication Date


  • 2017

Citation


  • Burrows, A. D., Chan, S., Gee, W. J., Mahon, M. F., Richardson, C., Sebestyen, V. M., Turski, D. & Warren, M. R. (2017). The impact of N, N′-ditopic ligand length and geometry on the structures of zinc-based mixed-linker metal-organic frameworks. CrystEngComm, 19 (37), 5549-5557.

Scopus Eid


  • 2-s2.0-85029952777

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=6035&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/4985

Number Of Pages


  • 8

Start Page


  • 5549

End Page


  • 5557

Volume


  • 19

Issue


  • 37

Place Of Publication


  • United Kingdom