HKUST-1

HKUST-1 (HKUST ⇒ Hong Kong University of Science and Technology),[1] which is also called MOF-199,[2] is a material in the class of metal-organic frameworks (MOFs). Metal-organic frameworks are crystalline materials, in which metals are linked by ligands (so-called linker molecules) to form repeating coordination motives extending in three dimensions. The HKUST-1 framework is built up of dimeric metal units, which are connected by benzene-1,3,5-tricarboxylate linker molecules. The paddlewheel unit is the commonly used structural motif to describe the coordination environment of the metal centers and also called secondary building unit (SBU) of the HKUST-1 structure. The paddlewheel is built up of four benzene-1,3,5-tricarboxylate linkers molecules, which bridge two metal centers. One water molecules is coordinated to each of the two metal centers at the axial position of the paddlewheel unit in the hydrated state, which is usually found if the material is handled in air. After an activation process (heating, vacuum), these water molecules can be removed (dehydrated state) and the coordination site at the metal atoms is left unoccupied. This unoccupied coordination site is called coordinatively unsaturated site (CUS) and can be accessed by other molecules.

Framework structure of desolvated HKUST-1. The spheres represent two different types of pores within the framework structure. Blue: metal, red: oxygen, black: carbon.
Paddlewheel unit (secondary building unit) of the HKUST-1 structure in the hydrated state. One water molecules is coordinated to each of metal center at the axial position.
Paddlewheel unit (secondary building unit) of the HKUST-1 structure in the dehydrated state. The axial positions at the metal centers are not occupied (= coordinatively unsaturated site, CUS).

Structural analogs

Monometallic HKUST-1 analogs

Cu2+ was used as metal center in the first synthesized HKUST-1 material,[1] but the HKUST-1 structure was also obtained with other metals. The oxidation state of most used metals is +II, which results in a neutral overall framework. In the case of trivalent metals (oxidation state +3), the overall framework is positively charged and requires anions to compensate the charge and guarantee charge neutrality.[3][4][5]

Overview of monometallic HKUST-1 analogs
Metal center and

oxidation state

 Year of first

publication

 Alternative

name

 Citation
Cu2+ 1999 Cu3BTC2

CuBTC

 [1][6]
Mo2+ 2006 TUDMOF-1 [7]
Fe2+/3+ 2007 [5]
Cr2+ 2010 [8]
Ni2+ 2011 [9]
Zn2+ 2011 [10]
Ru2+/3+ 2011 [4]
Mn2+ 2012 [11]
Fe2+ 2012 [11]
Co2+ 2012 [11]
Fe3+ 2014 [3]
Ru2+ 2016 [12]
Fe2+ 2019 [13]

Mixed-metal HKUST-1 analogs

In addition to monometallic HKUST-1 analogs, several mixed-metal HKUST-1 materials were synthesized, in which two metals are incorporated into the framework structure at crystallographically equivalent positions. The incorporation of two metals can be achieved by using both metals for the synthesis (direct synthesis) or by using post-synthetic metal-exchange. For the post-synthetic metal exchange, a monometallic HKUST-1 material is synthesized in the first step. Subsequently, this monometallic HKUST-1 is suspended in a solution containing the second metal, which results in an exchange of metal centers in the framework leading to a mixed-metal HKUST-1.

Overview of mixed-metal HKUST-1 analogs
Metal centers and

oxidation states

 Metal ratios

[-]

 Synthesis method Citation
Cu2+ / Zn2+ 0.99 : 0.01 Direct synthesis [14]
0.99 : 0.01

0.97 : 0.03

0.95 : 0.05

0.90 : 0.10

0.79 : 0.21

 [15]
0.95 : 0.05

0.90 : 0.10

 Direct synthesis

ball milling (mechanochemical)

 [16]
Cu2+ / Ni2+ 0.70 : 0.30

0.50 : 0.50

0.20 : 0.80

 Direct synthesis [17]
Cu2+ / Ru3+ 0.92 : 0.08 Direct synthesis [18]
Cu2+ / Ag+ not reported Post-synthetic metal-exchange [19]
Cu2+ / Mn2+ 0.94 : 0.06 Post-synthetic metal-exchange [20]
Cu2+ / Fe3+ 0.86 : 0.14 Post-synthetic metal-exchange [20]
Cu2+ / Co2+ 0.74 : 0.26 Post-synthetic metal-exchange [20]
Cu2+ / Pd2+ 0.91 : 0.09

0.86 : 0.14

0.80 : 0.20

 Direct synthesis [21]
0.81 : 0.19

0.59 : 0.41

 [22]
Ru2+/3+ / Rh2+ 0.95 : 0.05

0.89 : 0.11

0.79 : 0.21

0.47 : 0.53

0.24 : 0.76

0.03 : 0.97

 Direct synthesis [23]
Cu2+ / Fe3+ 0.69 : 0.31 Direct synthesis [24]
Cu2+ / Zn2+ / Mo6+ 0.80 : 0.15 : 0.05

0.70 : 0.15 : 0.15

0.55 : 0.15 : 0.30

 Direct synthesis

ball milling (mechanochemical)

 [16]

Theoretically calculated HKUST-1 analogs

Several HKUST-1 analogs have already been synthesized, but several research groups have investigated the properties of the HKUST-1 structure by means of theoretical calculations.[25][26][27][28][29][30] For this purpose, additional metal centers were incorporated into the framework on the theoretical level, which have not been used for the synthesis (e.g. Sc, V, Ti, W, Cd).[27][28] Theoretical study on a mixed-metal HKUST-1 containing Cu in combination with various other metals (e.g. W, Re, Os, Ir, Pt, Au) were also reported, of which several metal combinations have not been synthesized.[29][30]

References
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  2. Britt, D.; Tranchemontagne, D.; Yaghi, O. M. (2008-08-19). "Metal-organic frameworks with high capacity and selectivity for harmful gases". Proceedings of the National Academy of Sciences. 105 (33): 11623–11627. Bibcode:2008PNAS..10511623B. doi:10.1073/pnas.0804900105. ISSN 0027-8424. PMC 2575308. PMID 18711128.
  3. Sotnik, S. A.; Kolotilov, S. V.; Kiskin, M. A.; Dobrokhotova, Zh. V.; Gavrilenko, K. S.; Novotortsev, V. M.; Eremenko, I. L.; Imshennik, V. K.; Maksimov, Yu. V.; Pavlishchuk, V. V. (April 2014). "Synthesis, crystal structure, and physicochemical properties of the new metal-organic framework — the iron(iii) complex with benzene-1,3,5-tricarboxylate". Russian Chemical Bulletin. 63 (4): 862–869. doi:10.1007/s11172-014-0522-x. ISSN 1066-5285. S2CID 95858713.
  4. Kozachuk, Olesia; Yusenko, Kirill; Noei, Heshmat; Wang, Yuemin; Walleck, Stephan; Glaser, Thorsten; Fischer, Roland A. (2011). "Solvothermal growth of a ruthenium metal–organic framework featuring HKUST-1 structure type as thin films on oxide surfaces". Chemical Communications. 47 (30): 8509–11. doi:10.1039/c1cc11107h. ISSN 1359-7345. PMID 21716991.
  5. Xie, Linhua; Liu, Shuxia; Gao, Chaoying; Cao, Ruige; Cao, Jianfang; Sun, Chunyan; Su, Zhongmin (2007-08-15). "Mixed-Valence Iron(II, III) Trimesates with Open Frameworks Modulated by Solvents". Inorganic Chemistry. 46 (19): 7782–7788. doi:10.1021/ic062273m. ISSN 0020-1669. PMID 17696421.
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  8. Murray, Leslie J.; Dinca, Mircea; Yano, Junko; Chavan, Sachin; Bordiga, Silvia; Brown, Craig M.; Long, Jeffrey R. (2010-06-16). "Highly-Selective and Reversible O 2 Binding in Cr 3 (1,3,5-benzenetricarboxylate) 2". Journal of the American Chemical Society. 132 (23): 7856–7857. doi:10.1021/ja1027925. ISSN 0002-7863. PMID 20481535.
  9. Maniam, Palanikumar; Stock, Norbert (2011-06-06). "Investigation of Porous Ni-Based Metal–Organic Frameworks Containing Paddle-Wheel Type Inorganic Building Units via High-Throughput Methods". Inorganic Chemistry. 50 (11): 5085–5097. doi:10.1021/ic200381f. ISSN 0020-1669. PMID 21539354.
  10. Feldblyum, Jeremy I.; Liu, Ming; Gidley, David W.; Matzger, Adam J. (2011-11-16). "Reconciling the Discrepancies between Crystallographic Porosity and Guest Access As Exemplified by Zn-HKUST-1". Journal of the American Chemical Society. 133 (45): 18257–18263. doi:10.1021/ja2055935. ISSN 0002-7863. PMID 22011056.
  11. Zhang, Zhenjie; Zhang, Linping; Wojtas, Lukasz; Eddaoudi, Mohamed; Zaworotko, Michael J. (2012-01-18). "Template-Directed Synthesis of Nets Based upon Octahemioctahedral Cages That Encapsulate Catalytically Active Metalloporphyrins". Journal of the American Chemical Society. 134 (2): 928–933. doi:10.1021/ja208256u. ISSN 0002-7863. PMID 22208770.
  12. Zhang, Wenhua; Freitag, Kerstin; Wannapaiboon, Suttipong; Schneider, Christian; Epp, Konstantin; Kieslich, Gregor; Fischer, Roland A. (2016-12-19). "Elaboration of a Highly Porous Ru II,II Analogue of HKUST-1". Inorganic Chemistry. 55 (24): 12492–12495. doi:10.1021/acs.inorgchem.6b02038. ISSN 0020-1669. PMID 27989180.
  13. Yue, Yanfeng; Arman, Hadi; Chen, Banglin (2019-05-17). "Air-Free Synthesis of a Ferrous Metal-Organic Framework Featuring HKUST-1 Structure and its Mössbauer Spectrum". Zeitschrift für anorganische und allgemeine Chemie. 645 (11): 797–800. doi:10.1002/zaac.201900066. ISSN 1521-3749. S2CID 182860287.
  14. Jee, Bettina; Eisinger, Konrad; Gul-E-Noor, Farhana; Bertmer, Marko; Hartmann, Martin; Himsl, Dieter; Pöppl, Andreas (2010-10-07). "Continuous Wave and Pulsed Electron Spin Resonance Spectroscopy of Paramagnetic Framework Cupric Ions in the Zn(II) Doped Porous Coordination Polymer Cu 3− x Zn x (btc) 2". The Journal of Physical Chemistry C. 114 (39): 16630–16639. doi:10.1021/jp105955w. ISSN 1932-7447.
  15. Gul-E-Noor, Farhana; Jee, Bettina; Mendt, Matthias; Himsl, Dieter; Pöppl, Andreas; Hartmann, Martin; Haase, Jürgen; Krautscheid, Harald; Bertmer, Marko (2012-10-04). "Formation of Mixed Metal Cu 3– x Zn x (btc) 2 Frameworks with Different Zinc Contents: Incorporation of Zn 2+ into the Metal–Organic Framework Structure as Studied by Solid-State NMR". The Journal of Physical Chemistry C. 116 (39): 20866–20873. doi:10.1021/jp3054857. ISSN 1932-7447.
  16. Lee, Su-Kyung; Hong, Do-Young; Jeong, Myung-Geun; Yoon, Ji Woong; Bae, Jongyoon; Kim, Young Dok; Chang, Jong-San; Hwang, Young Kyu (2017-11-15). "Trimetallic copper trimesate with isomorphously substituted Mo(VI) and its catalytic properties". Microporous and Mesoporous Materials. 253: 223–232. doi:10.1016/j.micromeso.2017.07.007.
  17. Hu, Jue; Yu, Huijing; Dai, Wei; Yan, Xiaoyang; Hu, Xin; Huang, He (2014). "Enhanced adsorptive removal of hazardous anionic dye "congo red" by a Ni/Cu mixed-component metal–organic porous material". RSC Adv. 4 (66): 35124–35130. doi:10.1039/C4RA05772D. ISSN 2046-2069.
  18. Gotthardt, Meike A.; Schoch, Roland; Wolf, Silke; Bauer, Matthias; Kleist, Wolfgang (2015). "Synthesis and characterization of bimetallic metal–organic framework Cu–Ru-BTC with HKUST-1 structure". Dalton Transactions. 44 (5): 2052–2056. doi:10.1039/C4DT02491E. ISSN 1477-9226. PMID 25518915.
  19. Sun, Zhiguo; Li, Gang; Zhang, Yue; Liu, Hai-ou; Gao, Xionghou (2015-01-10). "Ag–Cu–BTC prepared by postsynthetic exchange as effective catalyst for selective oxidation of toluene to benzaldehyde". Catalysis Communications. 59: 92–96. doi:10.1016/j.catcom.2014.09.047.
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