Heterogenization of [Ru(bpy)3]Cl2 on Ordered Mesoporous Silica Materials for Photocatalytic Applications

Malik Sebbat; Anish Lazar; Claire Laurent; Christelle Despas; Neus Vilà; Alain Walcarius; Nathan McClenaghan; Emmanuel Oheix; Bénédicte Lebeau; Morgan Cormier; Jean-Philippe Goddard

doi:10.1055/a-2317-3672

Synlett, Table of Contents

Synlett 2025; 36(04): 335-340
DOI: 10.1055/a-2317-3672

letter

Heterogenization of [Ru(bpy)₃]Cl₂ on Ordered Mesoporous Silica Materials for Photocatalytic Applications

Malik Sebbat

^aUniversité de Haute-Alsace (UHA), Université de Strasbourg, CNRS, Laboratoire d’Innovation Moléculaire et Application (LIMA), UMR 7042, 68100 Mulhouse, France

,

Anish Lazar

^bUniversité de Haute Alsace, CNRS, IS2M, UMR 7361, 68100 Mulhouse, France

^cUniversité de Strasbourg, 6700 Strasbourg, France

,

Claire Laurent

^aUniversité de Haute-Alsace (UHA), Université de Strasbourg, CNRS, Laboratoire d’Innovation Moléculaire et Application (LIMA), UMR 7042, 68100 Mulhouse, France

,

Christelle Despas

^dUniversité de Lorraine, CNRS, Laboratoire de Chimie Physique et Microbiologie pour les Matériaux et l’Environnement (LCPME), 54000 Nancy, France

,

Neus Vilà

^dUniversité de Lorraine, CNRS, Laboratoire de Chimie Physique et Microbiologie pour les Matériaux et l’Environnement (LCPME), 54000 Nancy, France

,

Alain Walcarius

^dUniversité de Lorraine, CNRS, Laboratoire de Chimie Physique et Microbiologie pour les Matériaux et l’Environnement (LCPME), 54000 Nancy, France

,

Nathan McClenaghan

^eUniversité de Bordeaux, CNRS, Institut des Sciences des Moléculaires (ISM), UMR 5255, 33405 Talence, France

,

Emmanuel Oheix

^bUniversité de Haute Alsace, CNRS, IS2M, UMR 7361, 68100 Mulhouse, France

^cUniversité de Strasbourg, 6700 Strasbourg, France

,

Bénédicte Lebeau∗

^bUniversité de Haute Alsace, CNRS, IS2M, UMR 7361, 68100 Mulhouse, France

^cUniversité de Strasbourg, 6700 Strasbourg, France

,

Morgan Cormier ∗

^aUniversité de Haute-Alsace (UHA), Université de Strasbourg, CNRS, Laboratoire d’Innovation Moléculaire et Application (LIMA), UMR 7042, 68100 Mulhouse, France

,

Jean-Philippe Goddard∗

^aUniversité de Haute-Alsace (UHA), Université de Strasbourg, CNRS, Laboratoire d’Innovation Moléculaire et Application (LIMA), UMR 7042, 68100 Mulhouse, France

› Author Affiliations

Abstract

All articles of this category

Abstract

Herein, the preparation and characterization of three Ru-based heterogeneous photocatalysts supported on ordered mesoporous silica materials are reported. The photocatalytic activity of these catalysts was evaluated through oxidation, reduction, cycloaddition, and carboxylation reactions and their efficiencies are comparable to the parent [Ru(bpy)₃]Cl₂ under homogeneous conditions. These photocatalysts are efficiently recovered even after five reaction cycles offering new opportunities in sustainable chemistry.

Keywords

heterogeneous photocatalysis - ordered mesoporous silica - [Ru(bpy)₃]Cl₂ - sustainable chemistry

Full Text

References

References and Notes
1 Anastas PT. Chem. Rev. 2007; 107: 2167

2a Candish L, Collins KD, Cook CG, Douglas JJ, Gomez-Suarez A, Jolit A, Keess S. Chem. Rev. 2022; 122: 2907
2b McAtee C, McClain EJ, Stephenson CR. J. Trends Chem. 2019; 1: 111
2c Shaw MH, Twilton J, Macmillan DW. C. J. Org. Chem. 2016; 81: 6898
2d Goddard J.-P, Ollivier C, Fensterbank L. Acc. Chem. Res. 2016; 49: 1924
2e Prier CK, Rankic DA, MacMillan DW. C. Chem. Rev. 2013; 113: 5322

3 Sellet N, Cormier M, Goddard J.-P. Org. Chem. Front. 2021; 8: 6783

4a Savateev A, Antonietti M. ACS Catal. 2018; 8: 9790
4b Lang X, Chen X, Zhao J. Chem. Soc. Rev. 2014; 43: 473

5a Rana P, Kaushik B, Solanki K, Mohan Saini K, Sharla RK. Chem. Commun. 2022; 58: 11354
5b Yakushev AA, Abel AS, Averin AD, Beletskaya IP, Cheprakov AV, Ziankou IS, Bonneviot L, Bessmertnykh-Lemeune A. Coord. Chem. Rev. 2022; 458: 214331
5c Hong MakC, Han X, Du M, Kai J.-J, Tsang KF, Jia G, Cheng K.-C, Shen H.-H, Hsu H.-Y. J. Mater. Chem. A 2021; 9: 4454

6 Santiago-Portillo A, Baldovi HG, Carbonell E, Navalon S, Alvaro M, Garcia H, Ferrer B. J. Phys. Chem. C 2018; 122: 29190

7a Peng H, Romero T, Papaefthimiou V, Bertani P, Ritleng V. Mol. Catal. 2023; 545: 113183
7b Wang C.-A, Han Y.-F, Nie K, Li Y.-W. Mater. Chem. Front. 2019; 3: 1909
7c Zhang X, Li Y, Hao X, Jin K, Zhang R, Duan C. Tetrahedron 2018; 74: 1742
7d Liang Y, Bergbreiter DE. Catal. Sci. Technol. 2016; 6: 215
7e Priyadarshani N, Liang Y, Suriboot J, Bazzi HS, Bergbreiter DE. ACS Macro Lett. 2013; 2: 571
7f Wang J.-L, Wang C, deKrafft KE, Lin W. ACS Catal. 2012; 2: 417

8a Blanchard V, Asbai Z, Cottet K, Boissonnat G, Port M, Amara Z.. Org. Process Res. Dev. 2020; 24: 822
8b Teixeira RI, de Lucas NC, Garden SJ, Lanterna AE, Scaiano JC. Catal. Sci. Technol. 2020; 10: 1273
8c Tambosco B, Segura K, Seyrig C, Cabrera D, Port M, Ferroud C, Amara Z. ACS Catal. 2018; 8: 4383

9 Soria-Castro SM, Lebeau B, Cormier M, Neunlist S, Daou J, Goddard J.-P. Eur. J. Org. Chem. 2020; 1572
10 Mahmoud N, Awassa J, Toufaily J, Lebeau B, Daou TJ, Cormier M, Goddard J.-P. Molecules 2023; 28: 549

11a Wang Y, Zhao D. Chem. Rev. 2007; 107: 2821
11b Hoffmann F, Cornelius M, Morelle J, Fröba M. Angew. Chem. Int. Ed. 2006; 45: 3216

12a Roja-Luna R, Castillo-Rodriguez M, Ruiz JR, Jiménez-Sanchidrian C, Esquivel D, Romero-Salguero FJ. Dalton Trans. 2022; 51: 18708
12b Waki M, Shirai S, Yamanaka K.-I, Maegawa Y, Inagaki S. RSC Adv. 2020; 10: 13960
12c Takeda H, Ohashi M, Goto Y, Ohsuna T, Tani T, Inagaki S. Adv. Funct. Mater. 2016; 26: 5068
12d Jana A, Mondal J, Borah P, Mondal S, Bhaumik A, Zhao Y. Chem. Commun. 2015; 51: 10746

13 Walcarius A, Nasraoui R, Wang Z, Qu F, Urganova V, Etienne M, Göllü M, Demir AS, Gajdzik J, Hempelmann R. Bioelectrochemistry 2011; 82: 46
14 Zhao D, Huo Q, Feng J, Chmelka BF, Stucky GD. J. Am. Chem. Soc. 1998; 120: 6024
15 Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS. Nature 1992; 359: 710
16 Vilà N, Ghanbaja J, Aubert E, Walcarius A. Angew. Chem. Int. Ed. 2014; 53: 2945
17 Despas C, Walcarius A, Bessière J. Langmuir 1999; 15: 3186
18 Condie AG, González-Gómez JC, Stephenson CR. J. J. Am. Chem. Soc. 2010; 132: 1464
19 General Procedure for Photocatalyzed Aza-Henry Reaction 2-(4-Methoxyphenyl)-1,2,3,4-tetrahydroisoquinoline (8, 59.83 mg, 0.25 mmol, 1 equiv) and PCat (0.0025 mmol, 1 mol%) were added in 1 mL of freshly distilled MeNO₂ in a flask equipped with a magnetic stir bar. The mixture was stirred at room temperature and irradiated with a blue LED (420 nm) at 5 cm for 24 h under air. The mixture was evaporated under vacuum and purified by column chromatography on silica gel (pentane/diethyl ether, 80:20, v/v) to afford 9 as a yellow oil.
20 Maity S, Zhu M, Shinabery RS, Zheng N. Angew. Chem. Int. Ed. 2012; 51: 222
21 General Procedure for the Photocatalyzed [3+2] Cycloaddition N-Cyclopropylaniline (10, 26.64 mg, 0.2 mmol, 1 equiv), PCat (0.004 mmol, 0.02 equiv), styrene (11, 0.11 mL, 1 mmol, 5 equiv), and 1.12 mL of distilled and degassed MeNO₂ were added in a flask. The mixture was stirred at room temperature and irradiated with a blue LED (420 nm) at 5 cm for 24 h under air. The mixture was filtered over a Celite® pad with diethyl ether, and the filtrate was evaporated under vacuum. The mixture was purified by column chromatography on silica gel (PE/EtOAc, 95:5, v/v) to afford 12 as a yellow oil (dr = 60:40).
22 Tucker JW, Narayanam JM. R, Krabbe SW, Stephenson CR. J. Org. Lett. 2010; 12: 368
23 General Procedure for Photocatalytic Reduction of Bromomalonate The corresponding substrate 13 (0.076 mmol, 1 equiv) and PCat (0.0008 mmol, 1 mol%) was added in a flask equipped with magnetic stir bar evacuated and back-filled with nitrogen (N₂) with 1 mL of freshly degassed DMF. Et₃N (0.021 mL, 0.15 mmol, 2 equiv) was added dropwise. The mixture was stirred at room temperature and irradiated with blue LED (420 nm) placed at 5 cm for 24 h. 25 mL of water were added, and the aqueous layer was extracted with diethyl ether (3 × 25 mL). The organic layers were combined, dried over MgSO₄, and evaporated under vacuum. Full conversions were observed for all the substrates, and the ratio of 14:15 was determined by ¹H NMR spectroscopy on the crude reaction.
24 Analytical Data for Dimethyl 2-[4-(1H-indol-1-yl)butyl]malonate (15b, n = 4) ¹H NMR (400 MHz, CDCl₃): δ = 7.66 (d, J = 7.9 Hz, 1 H), 7.39–7.32 (m, 1 H), 7.24 (d, J = 1.1 Hz, 1 H), 7.18–7.07 (m, 2 H), 6.52 (dd, J = 3.1, 0.6 Hz, 1 H), 4.13 (t, J = 7.0 Hz, 2 H), 3.73 (s, 6 H), 3.35 (t, J = 7.4 Hz, 1 H), 2.01–1.84 (m, 4 H), 1.36 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 169.7, 135.8, 128.6, 127.8, 121.4,121.0, 119.2, 109.3, 101.0, 52.5, 51.4, 45.9, 29.7, 28.3, 24.6. FT-IR (neat): 3026, 2951, 2865, 1730, 1511, 1462, 1434, 1335, 1313, 1243, 1226, 1195, 1148, 1010, 739 cm^–1. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₇H₂₁NaO₄Na: 326.1363; found: 326.1357.
25 Analytical Data for Dimethyl 2-[5-(1H-indol-1-yl)pentyl]malonate (15c, n = 5) ¹H NMR (400 MHz, CDCl₃): δ = 7.69 (d, J = 7.9 Hz, 1 H), 7.38 (d, J = 8.3 Hz, 1 H), 7.30–7.20 (m, 1 H), 7.19–7.08 (m, 2 H), 6.54 (d, J = 3.1 Hz, 1 H), 4.12 (t, J = 7.0 Hz, 2 H), 3.76 (s, 6 H), 3.38 (t, J = 7.5 Hz, 1 H), 1.89 (ddd, J = 20.1, 8.8, 5.5 Hz, 4 H), 1.44–1.30 (m, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 169.7, 135.8, 128.5, 127.7, 121.3, 120.9, 119.1, 109.3, 100.9, 52.4, 51.5, 46.0, 29.8, 28.6, 26.8, 26.5. FT-IR (neat): 3023, 2952, 2862, 1731, 1511, 1484, 1462, 1435, 1313, 1253, 1200, 1153, 1047, 1012, 740 cm^–1. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₈H₂₃NO₄Na: 340.1519; found: 340.1516.
26 Yin Z.-B, Ye J.-H, Zhou W.-J, Zhang Y.-H, Ding L, Gui Y.-Y, Yan S.-S, Li J, Yu D.-G. Org. Lett. 2018; 20: 190
27 General Procedure for Photocatalytic for Oxy-Difluoroalkylation Compound 16 (45 mg, 0.20 mmol, 1 equiv), PCat (0.001 mmol, 0.5 mol%) and DABCO (0.039 mL, 0.4 mmol, 2 equiv) were added in 2.2 mL of anhydrous DMF (previously degassed with CO₂) into a Schlenk tube equipped with magnetic stir bar evacuated and backfilled with nitrogen (N₂). Then BrCF₂CO₂Et (0.038 mL, 0.3 mmol, 1.5 equiv) was added dropwise then CO₂ was bubbled into the solution. The mixture was stirred at room temperature and irradiated with a blue LED (420 nm) placed at 5 cm for 16 h. 25 mL of brine were added and the aqueous layer was extracted with EtOAc (3 × 25 mL). The organic layers were combined, dried over MgSO₄ and evaporated under vacuum. The mixture was purified by column chromatography on silica gel (PE/EtOAc, 80: 20, v/v) to afford 17 as a white solid.
28 Yeung CS. Angew. Chem. Int. Ed. 2019; 58: 5492

Supplementary Material

Supporting Information