Synergistic Induction of Solvent and Ligand-Substitution in Single-Crystal to Single-Crystal Transformations toward a MOF with Photocatalytic Dye Degradation

Nippich Kaeosamut; Pemika Chaichana; Athis Watwiangkham; Suwit Suthirakun; Suttipong Wannapaiboon; Nithiwat Sammawipawekul; Yothin Chimupala; Saranphong Yimklan

doi:10.1021/acs.inorgchem.3c01958

Synergistic Induction of Solvent and Ligand-Substitution in Single-Crystal to Single-Crystal Transformations toward a MOF with Photocatalytic Dye Degradation

Inorg Chem. 2023 Dec 11;62(49):19908-19921. doi: 10.1021/acs.inorgchem.3c01958. Epub 2023 Nov 27.

Authors

Nippich Kaeosamut^{1

2}, Pemika Chaichana³, Athis Watwiangkham⁴, Suwit Suthirakun⁴, Suttipong Wannapaiboon⁵, Nithiwat Sammawipawekul¹, Yothin Chimupala^{3

6

7}, Saranphong Yimklan^{1

6

7}

Affiliations

¹ Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand.
² Department of Chemistry, Faculty of Science and Engineering, University of Manchester, Manchester, M13 9PL, United Kingdom.
³ Research Laboratory of Pollution Treatment and Environmental Materials, Department of Industrial Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand.
⁴ School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima 30000, Thailand.
⁵ Synchrotron Light Research Institute, 111 University Avenue, Suranaree, Nakhon Ratchasima 30000, Thailand.
⁶ Center of Excellence in Materials Science and Technology, Chiang Mai University, Chiang Mai, 50200, Thailand.
⁷ Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand.

PMID: 38011001
DOI: 10.1021/acs.inorgchem.3c01958

Abstract

External-stimuli responsiveness as found in natural organisms and smart materials is attractive for functional materials scientists who attempt to design and imitate fascinating behavior into their materials. Herein, we report a couple of new solvent-responsive isostructural two-dimensional cationic metal-organic frameworks (MOFs) of Mn(II) (1a) and Zn(II) (2a) that undergo unprecedented single-crystal to single-crystal (SCSC) transformation toward the corresponding isostructural three-dimensional MOFs of Mn(II) (1b) and Zn(II) (2b). The 2D MOFs 1a and 2a have been effortlessly and rapidly synthesized via the microwave-heating technique. The SCSC transformations are synergistically induced by solvent and ligand-substitution reactions and able to be triggered by water, methanol, ethanol, and n-propanol. Time-dependent SCSC transformations were studied by in situ X-ray diffraction. Investigations on photodegradation of methyl orange showed that Zn-MOF 2b has higher efficiency than Mn-MOF 1b under UV-C irradiation at 300 min, 94.27%, and 21.91%, respectively. The influence of charge on the dye molecules, heterogeneity of the catalysis, and ^•OH radical-scavenging test was studied. First-principles computations suggest that the high photocatalytic activity of 2b may be attributed to its suitable band-edge position for redox reactions.