DUT-5

File:DUT-5 PerspectiveView CrossSection.png

File:DUT-5 OrthographicView M-OH-chain.png 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.{{Cite journal|last1=Senkovska|first1=Irena|last2=Hoffmann|first2=Frank|last3=Fröba|first3=Michael|last4=Getzschmann|first4=Juergen|last5=Böhlmann|first5=Winfried|last6=Kaskel|first6=Stefan|date=June 2009|title=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)|journal=Microporous and Mesoporous Materials|language=en|volume=122|issue=1–3|pages=93–98|doi=10.1016/j.micromeso.2009.02.020}}{{Cite journal|last1=Millange|first1=Franck|last2=Walton|first2=Richard I.|date=October 2018|title=MIL-53 and its Isoreticular Analogues: a Review of the Chemistry and Structure of a Prototypical Flexible Metal-Organic Framework|journal=Israel Journal of Chemistry|language=en|volume=58|issue=9–10|pages=1019–1035|doi=10.1002/ijch.201800084|s2cid=105480508 }} 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, but other isostructural materials, whose structures are comparable to DUT-5, have also been prepared with metals having oxidation states of +II or +IV .

class="wikitable"

|+Overview of non-functionalized DUT-5 analogs

!Name

!Metal center and oxidation state

!Year of first report

!Citation

DUT-5(Al)

|Al³⁺

|2009

COMOC-2

|V³⁺/V⁴⁺, V⁴⁺

|2013

|{{Cite journal|last1=Liu|first1=Ying-Ya|last2=Couck|first2=Sarah|last3=Vandichel|first3=Matthias|last4=Grzywa|first4=Maciej|last5=Leus|first5=Karen|last6=Biswas|first6=Shyam|last7=Volkmer|first7=Dirk|last8=Gascon|first8=Jorge|last9=Kapteijn|first9=Freek|last10=Denayer|first10=Joeri F. M.|last11=Waroquier|first11=Michel|date=2013-01-07|title=New V IV -Based Metal–Organic Framework Having Framework Flexibility and High CO 2 Adsorption Capacity|journal=Inorganic Chemistry|language=en|volume=52|issue=1|pages=113–120|doi=10.1021/ic301338a|pmid=23256823|issn=0020-1669}}

Mg(4S-PNO)(BPDC)

|Mg²⁺

|2018

|{{Cite journal|last1=Kunicki|first1=Hannah|last2=Chamberlain|first2=Thomas W.|last3=Clarkson|first3=Guy J.|last4=Kashtiban|first4=Reza J.|last5=Hooper|first5=Joseph E.|last6=Dawson|first6=Daniel M.|last7=Ashbrook|first7=Sharon E.|last8=Walton|first8=Richard I.|date=2018|title=An expanded MIL-53-type coordination polymer with a reactive pendant ligand|url=http://xlink.rsc.org/?DOI=C8CE00891D|journal=CrystEngComm|language=en|volume=20|issue=31|pages=4355–4358|doi=10.1039/C8CE00891D|issn=1466-8033|doi-access=free|hdl=10023/15542|hdl-access=free}}

Co(4S-PNO)(BPDC)

|Co²⁺

|2018

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{{Cite journal|last1=Yildiz|first1=Ceylan|last2=Kutonova|first2=Ksenia|last3=Oßwald|first3=Simon|last4=Titze‐Alonso|first4=Alba|last5=Bitzer|first5=Johannes|last6=Bräse|first6=Stefan|last7=Kleist|first7=Wolfgang|date=2020-02-20|title=Post‐synthetic Modification of DUT‐5‐based Metal Organic Frameworks for the Generation of Single‐site Catalysts and their Application in Selective Epoxidation Reactions|journal=ChemCatChem|language=en|volume=12|issue=4|pages=1134–1142|doi=10.1002/cctc.201901434|issn=1867-3880|doi-access=free}}{{Cite journal|last1=Liu|first1=Ying-Ya|last2=Decadt|first2=Roel|last3=Bogaerts|first3=Thomas|last4=Hemelsoet|first4=Karen|last5=Kaczmarek|first5=Anna M.|last6=Poelman|first6=Dirk|last7=Waroquier|first7=Michel|last8=Van Speybroeck|first8=Veronique|last9=Van Deun|first9=Rik|last10=Van Der Voort|first10=Pascal|date=2013-05-30|title=Bipyridine-Based Nanosized Metal–Organic Framework with Tunable Luminescence by a Postmodification with Eu(III): An Experimental and Theoretical Study|journal=The Journal of Physical Chemistry C|language=en|volume=117|issue=21|pages=11302–11310|doi=10.1021/jp402154q|issn=1932-7447}}{{Cite journal|last1=Bloch|first1=Eric D.|last2=Britt|first2=David|last3=Lee|first3=Chain|last4=Doonan|first4=Christian J.|last5=Uribe-Romo|first5=Fernando J.|last6=Furukawa|first6=Hiroyasu|last7=Long|first7=Jeffrey R.|last8=Yaghi|first8=Omar M.|date=2010-10-20|title=Metal Insertion in a Microporous Metal−Organic Framework Lined with 2,2′-Bipyridine|journal=Journal of the American Chemical Society|language=en|volume=132|issue=41|pages=14382–14384|doi=10.1021/ja106935d|pmid=20849109 |issn=0002-7863}} to further modify the framework structure after the initial synthesis or to alter the adsorption properties.{{Cite journal|last1=Wang|first1=Guangbo|last2=Leus|first2=Karen|last3=Couck|first3=Sarah|last4=Tack|first4=Pieter|last5=Depauw|first5=Hannes|last6=Liu|first6=Ying-Ya|last7=Vincze|first7=Laszlo|last8=Denayer|first8=Joeri F. M.|last9=Van Der Voort|first9=Pascal|date=2016|title=Enhanced gas sorption and breathing properties of the new sulfone functionalized COMOC-2 metal organic framework|url=http://xlink.rsc.org/?DOI=C6DT01355D|journal=Dalton Transactions|language=en|volume=45|issue=23|pages=9485–9491|doi=10.1039/C6DT01355D|pmid=27192612|issn=1477-9226|url-access=subscription}}

class="wikitable" \|+Overview of functionalized DUT-5 analogs ! rowspan="2" \|Functional linker ! colspan="3" \|Metal center
Al !V !Ga
File:2,2'-Bipyridine-5,5'-dicarboxylate.svg 2,2'-Bipyridine-5,5'-dicarboxylate \| MOF-253 \| - \| COMOC-4
File:4,4'-Bibenzoic acid-2,2'-sulfone.svg 4,4'-Bibenzoic acid-2,2'-sulfone \|{{Cite journal\|last1=Couck\|first1=Sarah\|last2=Liu\|first2=Ying-Ya\|last3=Leus\|first3=Karen\|last4=Baron\|first4=Gino V.\|last5=Van der Voort\|first5=Pascal\|last6=Denayer\|first6=Joeri F.M.\|date=April 2015\|title=Gas phase adsorption of alkanes, alkenes and aromatics on the sulfone-DUT-5 Metal Organic Framework\|journal=Microporous and Mesoporous Materials\|language=en\|volume=206\|pages=217–225\|doi=10.1016/j.micromeso.2014.11.028}}{{Cite journal\|last1=Halis\|first1=Selda\|last2=Reimer\|first2=Nele\|last3=Klinkebiel\|first3=Arne\|last4=Lüning\|first4=Ulrich\|last5=Stock\|first5=Norbert\|date=November 2015\|title=Four new Al-based microporous metal-organic framework compounds with MIL-53-type structure containing functionalized extended linker molecules\|journal=Microporous and Mesoporous Materials\|language=en\|volume=216\|pages=13–19\|doi=10.1016/j.micromeso.2015.01.030}} \| \|-
File:2-amino-1,1'-biphenyl-4,4'-dicarboxylate.svg 2-amino-[1,1']-biphenyl-4,4'-dicarboxylate \|{{Cite journal\|last1=Gotthardt\|first1=Meike A.\|last2=Grosjean\|first2=Sylvain\|last3=Brunner\|first3=Tobias S.\|last4=Kotzel\|first4=Johannes\|last5=Gänzler\|first5=Andreas M.\|last6=Wolf\|first6=Silke\|last7=Bräse\|first7=Stefan\|last8=Kleist\|first8=Wolfgang\|date=2015\|title=Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal–organic frameworks based on DUT-5\|url=http://xlink.rsc.org/?DOI=C5DT02276B\|journal=Dalton Transactions\|language=en\|volume=44\|issue=38\|pages=16802–16809\|doi=10.1039/C5DT02276B\|pmid=26336838\|issn=1477-9226\|doi-access=free}} \|- \|-
File:2-Ethynyl-1,1'-biphenyl-4,4'-dicarboxylate.svg 2-ethynyl-[1,1']-biphenyl-4,4'-dicarboxylate \| \|- \|-
File:2-azido-1,1'-biphenyl-4,4'-dicarboxylate.svg 2-azido-[1,1']-biphenyl-4,4'-dicarboxylate \| \|- \|-
File:2-nitro-1,1'-biphenyl-4,4'-dicarboxylate.svg 2-nitro-[1,1']-biphenyl-4,4'-dicarboxylate \| \|- \|-
File:2-iodo-1,1'-biphenyl-4,4'-dicarboxylate.svg 2-iodo-[1,1']-biphenyl-4,4'-dicarboxylate \|{{Cite journal\|last1=Tahmouresilerd\|first1=Babak\|last2=Moody\|first2=Michael\|last3=Agogo\|first3=Louis\|last4=Cozzolino\|first4=Anthony F.\|date=2019\|title=The impact of an isoreticular expansion strategy on the performance of iodine catalysts supported in multivariate zirconium and aluminum metal–organic frameworks\|url=http://xlink.rsc.org/?DOI=C9DT00368A\|journal=Dalton Transactions\|language=en\|volume=48\|issue=19\|pages=6445–6454\|doi=10.1039/C9DT00368A\|pmid=31017171\|s2cid=129944197 \|issn=1477-9226\|url-access=subscription}} \|- \|-

class="wikitable"

|+Overview of functionalized DUT-5 analogs

! rowspan="2" |Functional linker

! colspan="3" |Metal center

!Ga

File:2,2'-Bipyridine-5,5'-dicarboxylate.svg

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

MOF-253

| -

COMOC-4

File:4,4'-Bibenzoic acid-2,2'-sulfone.svg

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

|{{Cite journal|last1=Couck|first1=Sarah|last2=Liu|first2=Ying-Ya|last3=Leus|first3=Karen|last4=Baron|first4=Gino V.|last5=Van der Voort|first5=Pascal|last6=Denayer|first6=Joeri F.M.|date=April 2015|title=Gas phase adsorption of alkanes, alkenes and aromatics on the sulfone-DUT-5 Metal Organic Framework|journal=Microporous and Mesoporous Materials|language=en|volume=206|pages=217–225|doi=10.1016/j.micromeso.2014.11.028}}{{Cite journal|last1=Halis|first1=Selda|last2=Reimer|first2=Nele|last3=Klinkebiel|first3=Arne|last4=Lüning|first4=Ulrich|last5=Stock|first5=Norbert|date=November 2015|title=Four new Al-based microporous metal-organic framework compounds with MIL-53-type structure containing functionalized extended linker molecules|journal=Microporous and Mesoporous Materials|language=en|volume=216|pages=13–19|doi=10.1016/j.micromeso.2015.01.030}}

File:2-amino-1,1'-biphenyl-4,4'-dicarboxylate.svg

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

|{{Cite journal|last1=Gotthardt|first1=Meike A.|last2=Grosjean|first2=Sylvain|last3=Brunner|first3=Tobias S.|last4=Kotzel|first4=Johannes|last5=Gänzler|first5=Andreas M.|last6=Wolf|first6=Silke|last7=Bräse|first7=Stefan|last8=Kleist|first8=Wolfgang|date=2015|title=Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal–organic frameworks based on DUT-5|url=http://xlink.rsc.org/?DOI=C5DT02276B|journal=Dalton Transactions|language=en|volume=44|issue=38|pages=16802–16809|doi=10.1039/C5DT02276B|pmid=26336838|issn=1477-9226|doi-access=free}}

File:2-Ethynyl-1,1'-biphenyl-4,4'-dicarboxylate.svg

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

File:2-azido-1,1'-biphenyl-4,4'-dicarboxylate.svg

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

File:2-nitro-1,1'-biphenyl-4,4'-dicarboxylate.svg

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

File:2-iodo-1,1'-biphenyl-4,4'-dicarboxylate.svg

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

|{{Cite journal|last1=Tahmouresilerd|first1=Babak|last2=Moody|first2=Michael|last3=Agogo|first3=Louis|last4=Cozzolino|first4=Anthony F.|date=2019|title=The impact of an isoreticular expansion strategy on the performance of iodine catalysts supported in multivariate zirconium and aluminum metal–organic frameworks|url=http://xlink.rsc.org/?DOI=C9DT00368A|journal=Dalton Transactions|language=en|volume=48|issue=19|pages=6445–6454|doi=10.1039/C9DT00368A|pmid=31017171|s2cid=129944197 |issn=1477-9226|url-access=subscription}}

References

Category:Metal-organic frameworks