The fascinating feature of metal-organic frameworks is that they can respond to external stimuli, unlike other inorganic materials. This feature corresponds to the framework's flexibility, which originates with the long-range crystalline order of the framework accompanied by cooperative structural transformability. We have synthesized a novel metal-organic framework comprised of Cu(I) nodes with pyrazine linkers and benzene-1,3,5-tricarboxylate acting as template anions, named CUCAM-1 [Cu(Py)2(BTC)]n. In the presence of polar solvent systems, CUCAM-1 undergoes an irreversible structural transformation to yield a mixed phase that consists of HKUST-1 [Cu3(BTC)2(H2O)3]n and another CUCAM-2 [Cu(Py)(BTC)]n MOFs, whose novel structure is successfully revealed by continuous rotation electron diffraction from the mixture. In this structural transformation, a new ligand exchange occurs where template anions become ligands, confirmed by single crystal X-ray analysis. Further, structural transformation and the mechanism are explained by ab initio molecular dynamics (AIMD) simulations. Interestingly, different halides (F-, Cl-, and Br-) can be accompanied to affect/control the composition of the second phase by favoring the formation of the HKUST-1 phase over CUCAM-2, which was evident by the powder X-ray diffraction studies. Furthermore, the structural transformation induced by I- resulted in a colorimetric response due to the formation of a new MOF CUCAM-3, paving the way for use as an iodide detector.

Center for Catalysis and Separations Khalifa University of Science and Technology P O Box 127788 Abu Dhabi United Arab Emirates

Department of Chemistry Khalifa University of Science and Technology P O Box 127788 Abu Dhabi United Arab Emirates

Department of Inorganic Chemistry Faculty of Science Charles University Hlavova 2030 128 00 Prague 2 Czech Republic

Department of Materials and Environmental Chemistry Stockholm University SE 106 91 Stockholm Sweden

Department of Physical and Macromolecular Chemistry Faculty of Science Charles University Hlavova 2030 128 00 Prague 2 Czech Republic

EaStCHEM School of Chemistry University of St Andrews St Andrews KY16 9ST U K

Technology development Cell Ben Guerir 43150 Morocco

See more in PubMed

Baumann A. E.; Burns D. A.; Liu B.; Thoi V. S. Metal-Organic Framework Functionalization and Design Strategies for Advanced Electrochemical Energy Storage Devices. Commun. Chem. 2019, 2 (1), 86.10.1038/s42004-019-0184-6. DOI

Wang M.; Dong R.; Feng X. Two-Dimensional Conjugated Metal-Organic Frameworks (2D -MOFs): Chemistry and Function for MOFtronics. Chem. Soc. Rev. 2021, 5 (4), 2764–2793. 10.1039/D0CS01160F. PubMed DOI

Mohideen M. I.; Lei C.; Tuek J. Í.; Malina O.; Brivio F.; Kasneryk V.; Huang Z.; Mazur M.; Zou X.; Nachtigall P.; Ejka J. Í.; Morris R. E. Magneto-Structural Correlations of Novel Kagomé-Type Metal Organic Frameworks. J. Mater. Chem. C: Mater. Opt. Electron. Dev. 2019, 7 (22), 6692–6697. 10.1039/C9TC01053J. DOI

El Mkami H.; Mohideen M. I. H.; Pal C.; McKinlay A.; Scheimann O.; Morris R. E. EPR and Magnetic Studies of a Novel Copper Metal Organic Framework (STAM-I). Chem. Phys. Lett. 2012, 544, 17–21. 10.1016/j.cplett.2012.06.012. DOI

Furukawa H.; Cordova K. E.; O’Keeffe M.; Yaghi O. M. The Chemistry and Applications of Metal-Organic Frameworks. Science (1979) 2013, 341 (6149), 123044410.1126/science.1230444. PubMed DOI

Kumar P.; Pournara A.; Kim K.-H.; Bansal V.; Rapti S.; Manos M. J. Metal-Organic Frameworks: Challenges and Opportunities for Ion-Exchange/Sorption Applications. Prog. Mater. Sci. 2017, 86, 25–74. 10.1016/j.pmatsci.2017.01.002. DOI

Mohideen M. I. H.; Belmabkhout Y.; Bhatt P. M.; Shkurenko A.; Chen Z.; Adil K.; Eddaoudi M. Upgrading Gasoline to High Octane Numbers Using a Zeolite-like Metal-Organic Framework Molecular Sieve with Ana-Topology. Chem. Commun. (Camb) 2018, 54 (68), 9414–9417. 10.1039/C8CC04824J. PubMed DOI

He Y.; Zhou W.; Qian G.; Chen B. Methane Storage in Metal-Organic Frameworks. Chem. Soc. Rev. 2014, 43 (16), 5657–5678. 10.1039/C4CS00032C. PubMed DOI

Mohideen M. I. H.; Pillai R. S.; Adil K.; Bhatt P. M.; Belmabkhout Y.; Shkurenko A.; Maurin G.; Eddaoudi M. A Fine-Tuned MOF for Gas and Vapor Separation: A Multipurpose Adsorbent for Acid Gas Removal, Dehydration, and BTX Sieving. Chem. 2017, 3 (5), 822–833. 10.1016/j.chempr.2017.09.002. DOI

Hanikel N.; Prévot M. S.; Yaghi O. M. MOF Water Harvesters. Nat. Nanotechnol 2020, 15 (5), 348–355. 10.1038/s41565-020-0673-x. PubMed DOI

Opanasenko M.; Dhakshinamoorthy A.; Hwang Y. K.; Chang J.; Garcia H.; Čejka J. Superior Performance of Metal–Organic Frameworks over Zeolites as Solid Acid Catalysts in the Prins Reaction: Green Synthesis of Nopol. ChemSusChem 2013, 6 (5), 865–871. 10.1002/cssc.201300032. PubMed DOI

Ding M.; Flaig R. W.; Jiang H.-L.; Yaghi O. M. Carbon Capture and Conversion Using Metal-Organic Frameworks and MOF-Based Materials. Chem. Soc. Rev. 2019, 48 (1), 2783–2828. 10.1039/C8CS00829A. PubMed DOI

Schneemann A.; Bon V.; Schwedler I.; Senkovska I.; Kaskel S.; Fischer R. A. Flexible Metal–Organic Frameworks. Chem. Soc. Rev. 2014, 43 (16), 6062–6096. 10.1039/C4CS00101J. PubMed DOI

Lee J. H.; Jeoung S.; Chung Y. G.; Moon H. R. Elucidation of Flexible Metal-Organic Frameworks: Research Progresses and Recent Developments. Coord. Chem. Rev. 2019, 389, 161–188. 10.1016/j.ccr.2019.03.008. DOI

Burrows A. D.; Kelly D. J.; Haja Mohideen M. I.; Mahon M. F.; Pop V. M.; Richardson C. Competition between Coordination and Hydrogen Bonding in Networks Constructed Using Dipyridyl-1H-Pyrazole Ligands. CrystEngComm 2011, 13 (5), 1676–1682. 10.1039/C0CE00310G. DOI

Mohideen M. I. H.; Xiao B.; Wheatley P. S.; McKinlay A. C.; Li Y.; Slawin A. M. Z.; Aldous D. W.; Cessford N. F.; Düren T.; Zhao X.; Gill R.; Thomas K. M.; Griffin J. M.; Ashbrook S. E.; Morris R. E. Protecting Group and Switchable Pore-Discriminating Adsorption Properties of a Hydrophilic-Hydrophobic Metal-Organic Framework. Nat. Chem. 2011, 3 (4), 304–310. 10.1038/nchem.1003. PubMed DOI

Férey G.; Serre C. Large Breathing Effects in Three-Dimensional Porous Hybrid Matter: Facts, Analyses, Rules and Consequences. Chem. Soc. Rev. 2009, 38 (5), 1380.10.1039/b804302g. PubMed DOI

Li J.; Huang P.; Wu X.-R.; Tao J.; Huang R.-B.; Zheng L.-S. Metal-Organic Frameworks Displaying Single Crystal-to-Single Crystal Transformation through Postsynthetic Uptake of Metal Clusters. Chem. Sci. 2013, 4 (8), 3232.10.1039/c3sc51379c. DOI

Wang H.; Meng W.; Wu J.; Ding J.; Hou H.; Fan Y. Crystalline Central-Metal Transformation in Metal-Organic Frameworks. Coord. Chem. Rev. 2016, 307, 130–146. 10.1016/j.ccr.2015.05.009. DOI

Lalonde M.; Bury W.; Karagiaridi O.; Brown Z.; Hupp J. T.; Farha O. K. Transmetalation: Routes to Metal Exchange within Metal–Organic Frameworks. J. Mater. Chem. A Mater. 2013, 1 (18), 5453.10.1039/c3ta10784a. DOI

Burnett B. J.; Barron P. M.; Hu C.; Choe W. Stepwise Synthesis of Metal–Organic Frameworks: Replacement of Structural Organic Linkers. J. Am. Chem. Soc. 2011, 133 (26), 9984–9987. 10.1021/ja201911v. PubMed DOI

Kaeosamut N.; Chimupala Y.; Yanu P.; Wannapaiboon S.; Sammawipawekul N.; Tonkaew S.; Jakmunee J.; Yimklan S. Ligand-Substitution-Induced Single-Crystal to Single-Crystal Transformations in a Redox-Versatile Cu(II) MOF toward Smartphone-Based Colorimetric Detection of Iodide. Inorg. Chem. 2022, 61 (48), 19612–19623. 10.1021/acs.inorgchem.2c03579. PubMed DOI

Chimupala Y.; Kaeosamut N.; Yimklan S. Octahedral to Tetrahedral Conversion upon a Ligand-Substitution-Induced Single-Crystal to Single-Crystal Transformation in a Rectangular Zn(II) Metal–Organic Framework and Its Photocatalysis. Cryst. Growth Des 2021, 21 (9), 5373–5382. 10.1021/acs.cgd.1c00658. DOI

Kaeosamut N.; Chimupala Y.; Yimklan S. Anion-Controlled Synthesis of Enantiomeric Twofold Interpenetrated 3D Zinc(II) Coordination Polymer with Ligand Substitution-Induced Single-Crystal-to-Single-Crystal Transformation and Photocatalysis. Cryst. Growth Des 2021, 21 (5), 2942–2953. 10.1021/acs.cgd.1c00103. DOI

Rani D.; Bhasin K. K.; Singh M. Non-Porous Interpenetrating Co-Bpe MOF for Colorimetric Iodide Sensing. Dalton Transactions 2021, 50 (38), 13430–13437. 10.1039/D1DT01757H. PubMed DOI

Chen Y.-Q.; Li G.-R.; Chang Z.; Qu Y.-K.; Zhang Y.-H.; Bu X.-H. A Cu(i) Metal–Organic Framework with 4-Fold Helical Channels for Sensing Anions. Chem. Sci. 2013, 4 (9), 3678.10.1039/c3sc00057e. DOI

Ding Y.-J.; Li T.; Hong X.-J.; Zhu L.-C.; Cai Y.-P.; Zhu S.-M.; Yu S.-J. Construction of Four 3d–4f Heterometallic Pillar-Layered Frameworks Containing Left- and Right-Handed Helical Chains and a I – Chemosensor. CrystEngComm 2015, 17 (21), 3945–3952. 10.1039/C5CE00324E. DOI

Shi P.-F.; Hu H.-C.; Zhang Z.-Y.; Xiong G.; Zhao B. Heterometal–Organic Frameworks as Highly Sensitive and Highly Selective Luminescent Probes to Detect I – Ions in Aqueous Solutions. Chem. Commun. 2015, 51 (19), 3985–3988. 10.1039/C4CC09081K. PubMed DOI

Qu G.; Han Y.; Qi J.; Xing X.; Hou M.; Sun Y.; Wang X.; Sun G. Rapid Iodine Capture from Radioactive Wastewater by Green and Low-Cost Biomass Waste Derived Porous Silicon–Carbon Composite. RSC Adv. 2021, 11 (9), 5268–5275. 10.1039/D0RA09723C. PubMed DOI PMC

Sheldrick G. M. SHELXT – Integrated Space-Group and Crystal-Structure Determination. Acta Crystallogr. A Found Adv. 2015, 71 (1), 3–8. 10.1107/S2053273314026370. PubMed DOI PMC

Sheldrick G. M. Crystal Structure Refinement with SHELXL. Acta Crystallogr. C Struct Chem. 2015, 71 (1), 3–8. 10.1107/S2053229614024218. PubMed DOI PMC

Spek A. L. PLATON SQUEEZE: A Tool for the Calculation of the Disordered Solvent Contribution to the Calculated Structure Factors. Acta Crystallogr. C Struct Chem. 2015, 71 (1), 9–18. 10.1107/S2053229614024929. PubMed DOI

Spek A. L. Structure Validation in Chemical Crystallography. Acta Crystallogr. D Biol. Crystallogr. 2009, 65 (2), 148–155. 10.1107/S090744490804362X. PubMed DOI PMC

Hutter J.; Iannuzzi M.; Schiffmann F.; VandeVondele J. cp2k: Atomistic Simulations of Condensed Matter Systems. WIREs Comput. Mol. Sci. 2014, 4 (1), 15–25. 10.1002/wcms.1159. DOI

VandeVondele J.; Krack M.; Mohamed F.; Parrinello M.; Chassaing T.; Hutter J. Quickstep: Fast and Accurate Density Functional Calculations Using a Mixed Gaussian and Plane Waves Approach. Comput. Phys. Commun. 2005, 167 (2), 103–128. 10.1016/j.cpc.2004.12.014. DOI

Perdew J. P.; Burke K.; Ernzerhof M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77 (18), 3865–3868. 10.1103/PhysRevLett.77.3865. PubMed DOI

Grimme S.; Antony J.; Ehrlich S.; Krieg H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132 (15), 154104.10.1063/1.3382344. PubMed DOI

VandeVondele J.; Hutter J. Gaussian Basis Sets for Accurate Calculations on Molecular Systems in Gas and Condensed Phases. J. Chem. Phys. 2007, 127 (11), 114105.10.1063/1.2770708. PubMed DOI

Hartwigsen C.; Goedecker S.; Hutter J. Relativistic Separable Dual-Space Gaussian Pseudopotentials from H to Rn. Phys. Rev. B 1998, 58 (7), 3641–3662. 10.1103/PhysRevB.58.3641. PubMed DOI

Goedecker S.; Teter M.; Hutter J. Separable Dual-Space Gaussian Pseudopotentials. Phys. Rev. B 1996, 54 (3), 1703–1710. 10.1103/PhysRevB.54.1703. PubMed DOI

Guo H.-X.; Weng W.; Li X.-Z.; Liang M.; Zheng C.-Q. A Novel Three-Dimensional Coordination Polymer Constructed from Pyrazine and Copper(I): Poly[[Copper(I)-Di-μ 2 -Pyrazine-κ 4N: N ′] 3,5-Dicarboxybenzenesulfonate Monohydrate]. Acta Crystallogr. C 2008, 64 (9), m314–m316. 10.1107/S0108270108025900. PubMed DOI

Ge M.; Wang Y.; Carraro F.; Liang W.; Roostaeinia M.; Siahrostami S.; Proserpio D. M.; Doonan C.; Falcaro P.; Zheng H.; Zou X.; Huang Z. High-Throughput Electron Diffraction Reveals a Hidden Novel Metal–Organic Framework for Electrocatalysis. Angew. Chem. 2021, 133 (20), 11492–11498. 10.1002/ange.202016882. PubMed DOI PMC

Gao C.; Liu S.; Xie L.; Sun C.; Cao J.; Ren Y.; Feng D.; Su Z. Rational Design Microporous Pillared-Layer Frameworks: Syntheses. Structures and Gas Sorption Properties. CrystEngComm 2009, 11 (1), 177–182. 10.1039/B812097H. DOI

Jeong S.; Kim D.; Shin S.; Moon D.; Cho S. J.; Lah M. S. Combinational Synthetic Approaches for Isoreticular and Polymorphic Metal–Organic Frameworks with Tuned Pore Geometries and Surface Properties. Chem. Mater. 2014, 26 (4), 1711–1719. 10.1021/cm404239s. DOI

Kühne T. D.; Iannuzzi M.; Del Ben M.; Rybkin V. V.; Seewald P.; Stein F.; Laino T.; Khaliullin R. Z.; Schütt O.; Schiffmann F.; Golze D.; Wilhelm J.; Chulkov S.; Bani-Hashemian M. H.; Weber V.; Borštnik U.; Taillefumier M.; Jakobovits A. S.; Lazzaro A.; Pabst H.; Müller T.; Schade R.; Guidon M.; Andermatt S.; Holmberg N.; Schenter G. K.; Hehn A.; Bussy A.; Belleflamme F.; Tabacchi G.; Glöß A.; Lass M.; Bethune I.; Mundy C. J.; Plessl C.; Watkins M.; VandeVondele J.; Krack M.; Hutter J. CP2K: An Electronic Structure and Molecular Dynamics Software Package—Quickstep: Efficient and Accurate Electronic Structure Calculations. J. Chem. Phys. 2020, 152 (19), 194103.10.1063/5.0007045. PubMed DOI

Majano G.; Martin O.; Hammes M.; Smeets S.; Baerlocher C.; Pérez-Ramírez J. Solvent-Mediated Reconstruction of the Metal–Organic Framework HKUST-1 (Cu3(BTC)2). Adv. Funct Mater. 2014, 24 (25), 3855–3865. 10.1002/adfm.201303678. DOI