Aryl sulfonium based novel multifunctional polyoxovanadate hybrid: photochromism and oxidative desulfurization (ODS) catalysis reaction Kousik Routh 1 and Prof. Dr. Chullikkattil P. Pradeep 2 1 School of Basic Sciences, Indian Institute of Technology Mandi, Kamand – 175005, Himachal Pradesh, India, *E-mail: pradeep@iitmandi.ac.in; Fax: +911905 267 009; Tel: +91 1905 267 045 Multifunctional materials exhibiting two or more different functional properties have recently received considerable attention because of their potential applications in diverse fields, including drug delivery, diagnosis, information storage, green catalysis, etc. 1 . Incorporating suitable organic functional moieties into metal oxides via ionic or supramolecular interactions, self-assembly, or intercalation is a successful strategy for multifunctional materials. 2 . In this study, we were interested in developing polyoxovanadates-based multifunctional hybrid materials for photochromic and catalytic ODS applications. Here we used a series of aryl sulfonium counter ions to tune the photochromic and catalytic properties of the hybrids simultaneously. The use of aryl sulfonium OCIs bearing an aromatic ring system and aldehydic functionalities help to tune the solubility of the POV-hybrids and hence their heterogenecity in the catalytic media. Further, we assumed that the incorporation of formyl group(s) next to the phenolic group on the counterions could provide certain advantages in inducing proton transfer to the cluster upon photoexcitation. 3 Accordingly, three POV-based aryl sulfonium hybrids, HY1-HY3, having the formula (FHPDS) 4 [H 2 V 10 O 28 ] (HY1) , (DFHPDS) 4 [H 2 V 10 O 28 ] (HY2) , (EFPDS) 4 [H 2 V 10 O 28 ] (HY3) (where FHPDS = (3-formyl- 4-hydroxyphenyl) dimethyl sulfonium, DFHPDS = (3,5-diformyl-4-hydroxyphenyl) dimethylsulfonium, EFPDS = (4-ethoxy-3-formylphenyl) dimethylsulfonium) were synthesized and characterised by several analytical and spectroscopic techniques including ESI-MS and single-crystal X-ray diffraction studies. The photochromic and catalytic ODS activities of these hybrids have been studied in detail and the results of these studies provide exciting new insights into the photochromic and ODS activities of POM-based hybrids in general and POV-based systems in particular.
Keywords: Polyoxovanadate, Aryl sulfonium ion, Multifunctional material, Photochromism, ODS catalysis. References 1. Kumar, A., Gupta, A. K., Devi, M., Gonsalves, K. E., & Pradeep, C. P. Inorg . Chem. , 2017 , 56 (17), 10325-10336. 2. Li, C.; Mizuno, N.; Yamaguchi, K.; Suzuki, K. J. Am. Chem. Soc. 2019, 141 (19), 7687-7692. 3. Moorthy, J. N.; Mal, P.; Natarajan, R.; Venugopalan, P. Org . Lett. 2001, 3 (10), 1579-1582.
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