Crystal structure of DUT-5. Perspective view of the pore cross-section. Metal: green, oxygen: red, carbon: grey, hydrogen: not shown.
Crystal structure of DUT-5. Orthographic view of the M-OH chains, which are connected by biphenyl-4,4'-dicarboxylate linker molecules. Metal: green, oxygen: red, carbon: grey, hydrogen: not shown.

DUT-5 (DUT ⇒ Dresden University of Technology) is a material in the class of metal-organic frameworks (MOFs). Metal-organic frameworks are crystalline materials, in which metals are linked by ligands (linker molecules) to form repeating three-dimensional structures known as coordination entities. The DUT-5 framework is an expanded version of the MIL-53 structure and consists of Al3+ metal centers and biphenyl-4,4'-dicarboxylate (BPDC) linker molecules.[1][2] It consists of inorganic [M-OH] chains, which are connected by the biphenyl-4,4'-dicarboxylate linkers to four neighboring inorganic chains. The resulting structure contains diamond-shaped micropores extending in one dimension.

Structural analogs

The DUT-5 structure was initially synthesized with Al3+ as metal center,[1] but other isostructural materials, whose structures are comparable to DUT-5, have also been prepared with metals having oxidation states of +II or +IV .

Overview of non-functionalized DUT-5 analogs
Name Metal center and oxidation state Year of first report Citation
DUT-5(Al) Al3+ 2009 [1]
COMOC-2 V3+/V4+, V4+ 2013 [3]
Mg(4S-PNO)(BPDC) Mg2+ 2018 [4]
Co(4S-PNO)(BPDC) Co2+ 2018 [4]

Due to the tool-box like design of metal-organic framework materials, other organic molecules, which are structurally similar to biphenyl-4,4'-dicarboxylate, have also been used as linker molecules for the synthesis of functionalized DUT-5 materials, which contain uncoordinated functional groups in their framework structure. For the functionalized DUT-5 materials, the additional functional groups at the functional biphenyl-4,4'dicarboxylate linkers in the DUT-5 framework have been used for post-synthetic modification reactions[5][6][7] to further modify the framework structure after the initial synthesis or to alter the adsorption properties.[8]

Overview of functionalized DUT-5 analogs
Functional linker Metal center
Al V Ga
2,2'-Bipyridine-5,5'-dicarboxylate

2,2'-Bipyridine-5,5'-dicarboxylate

 [7]

MOF-253

 - [6]

COMOC-4

4,4'-Bibenzoic acid-2,2'-sulfone

4,4'-Bibenzoic acid-2,2'-sulfone

 [9][10] [8] -
2-amino-1,1'-biphenyl-4,4'-dicarboxylate

2-amino-[1,1']-biphenyl-4,4'-dicarboxylate

 [11][10] - -
2-Ethynyl-1,1'-biphenyl-4,4'-dicarboxylate

2-ethynyl-[1,1']-biphenyl-4,4'-dicarboxylate

 [11] - -
2-azido-1,1'-biphenyl-4,4'-dicarboxylate

2-azido-[1,1']-biphenyl-4,4'-dicarboxylate

 [11] - -
2-nitro-1,1'-biphenyl-4,4'-dicarboxylate

2-nitro-[1,1']-biphenyl-4,4'-dicarboxylate

 [11][10] - -
2-iodo-1,1'-biphenyl-4,4'-dicarboxylate

2-iodo-[1,1']-biphenyl-4,4'-dicarboxylate

 [12] - -

References

  1. 1 2 3 Senkovska, Irena; Hoffmann, Frank; Fröba, Michael; Getzschmann, Juergen; Böhlmann, Winfried; Kaskel, Stefan (June 2009). "New highly porous aluminium based metal-organic frameworks: Al(OH)(ndc) (ndc=2,6-naphthalene dicarboxylate) and Al(OH)(bpdc) (bpdc=4,4′-biphenyl dicarboxylate)". Microporous and Mesoporous Materials. 122 (1–3): 93–98. doi:10.1016/j.micromeso.2009.02.020.
  2. ↑ Millange, Franck; Walton, Richard I. (October 2018). "MIL-53 and its Isoreticular Analogues: a Review of the Chemistry and Structure of a Prototypical Flexible Metal-Organic Framework". Israel Journal of Chemistry. 58 (9–10): 1019–1035. doi:10.1002/ijch.201800084. S2CID 105480508.
  3. ↑ Liu, Ying-Ya; Couck, Sarah; Vandichel, Matthias; Grzywa, Maciej; Leus, Karen; Biswas, Shyam; Volkmer, Dirk; Gascon, Jorge; Kapteijn, Freek; Denayer, Joeri F. M.; Waroquier, Michel (2013-01-07). "New V IV -Based Metal–Organic Framework Having Framework Flexibility and High CO 2 Adsorption Capacity". Inorganic Chemistry. 52 (1): 113–120. doi:10.1021/ic301338a. ISSN 0020-1669. PMID 23256823.
  4. 1 2 Kunicki, Hannah; Chamberlain, Thomas W.; Clarkson, Guy J.; Kashtiban, Reza J.; Hooper, Joseph E.; Dawson, Daniel M.; Ashbrook, Sharon E.; Walton, Richard I. (2018). "An expanded MIL-53-type coordination polymer with a reactive pendant ligand". CrystEngComm. 20 (31): 4355–4358. doi:10.1039/C8CE00891D. hdl:10023/15542. ISSN 1466-8033.
  5. ↑ Yildiz, Ceylan; Kutonova, Ksenia; Oßwald, Simon; Titze‐Alonso, Alba; Bitzer, Johannes; Bräse, Stefan; Kleist, Wolfgang (2020-02-20). "Post‐synthetic Modification of DUT‐5‐based Metal Organic Frameworks for the Generation of Single‐site Catalysts and their Application in Selective Epoxidation Reactions". ChemCatChem. 12 (4): 1134–1142. doi:10.1002/cctc.201901434. ISSN 1867-3880.
  6. 1 2 Liu, Ying-Ya; Decadt, Roel; Bogaerts, Thomas; Hemelsoet, Karen; Kaczmarek, Anna M.; Poelman, Dirk; Waroquier, Michel; Van Speybroeck, Veronique; Van Deun, Rik; Van Der Voort, Pascal (2013-05-30). "Bipyridine-Based Nanosized Metal–Organic Framework with Tunable Luminescence by a Postmodification with Eu(III): An Experimental and Theoretical Study". The Journal of Physical Chemistry C. 117 (21): 11302–11310. doi:10.1021/jp402154q. ISSN 1932-7447.
  7. 1 2 Bloch, Eric D.; Britt, David; Lee, Chain; Doonan, Christian J.; Uribe-Romo, Fernando J.; Furukawa, Hiroyasu; Long, Jeffrey R.; Yaghi, Omar M. (2010-10-20). "Metal Insertion in a Microporous Metal−Organic Framework Lined with 2,2′-Bipyridine". Journal of the American Chemical Society. 132 (41): 14382–14384. doi:10.1021/ja106935d. ISSN 0002-7863. PMID 20849109.
  8. 1 2 Wang, Guangbo; Leus, Karen; Couck, Sarah; Tack, Pieter; Depauw, Hannes; Liu, Ying-Ya; Vincze, Laszlo; Denayer, Joeri F. M.; Van Der Voort, Pascal (2016). "Enhanced gas sorption and breathing properties of the new sulfone functionalized COMOC-2 metal organic framework". Dalton Transactions. 45 (23): 9485–9491. doi:10.1039/C6DT01355D. ISSN 1477-9226. PMID 27192612.
  9. ↑ Couck, Sarah; Liu, Ying-Ya; Leus, Karen; Baron, Gino V.; Van der Voort, Pascal; Denayer, Joeri F.M. (April 2015). "Gas phase adsorption of alkanes, alkenes and aromatics on the sulfone-DUT-5 Metal Organic Framework". Microporous and Mesoporous Materials. 206: 217–225. doi:10.1016/j.micromeso.2014.11.028.
  10. 1 2 3 Halis, Selda; Reimer, Nele; Klinkebiel, Arne; Lüning, Ulrich; Stock, Norbert (November 2015). "Four new Al-based microporous metal-organic framework compounds with MIL-53-type structure containing functionalized extended linker molecules". Microporous and Mesoporous Materials. 216: 13–19. doi:10.1016/j.micromeso.2015.01.030.
  11. 1 2 3 4 Gotthardt, Meike A.; Grosjean, Sylvain; Brunner, Tobias S.; Kotzel, Johannes; Gänzler, Andreas M.; Wolf, Silke; Bräse, Stefan; Kleist, Wolfgang (2015). "Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal–organic frameworks based on DUT-5". Dalton Transactions. 44 (38): 16802–16809. doi:10.1039/C5DT02276B. ISSN 1477-9226. PMID 26336838.
  12. ↑ Tahmouresilerd, Babak; Moody, Michael; Agogo, Louis; Cozzolino, Anthony F. (2019). "The impact of an isoreticular expansion strategy on the performance of iodine catalysts supported in multivariate zirconium and aluminum metal–organic frameworks". Dalton Transactions. 48 (19): 6445–6454. doi:10.1039/C9DT00368A. ISSN 1477-9226. PMID 31017171. S2CID 129944197.
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