A Phosphonate Substituent in a 1,10‐Phenanthroline Ligand Boosts Light‐Driven Catalytic Water Oxidation Performance Sensitized by Ruthenium Chromophores

Abstract

A series of new Ruthenium(II) complexes based on the (1,10phenanthrolin-5-yl)diethyl phosphonate ligand L2 and their corresponding phosphonic acid along with reference compounds are synthesized in order to evaluate the influence of the phosphonate substitution on the catalytic performance of such molecules. UV-vis absorption and emission spectroscopy show, that introduction of a phosphonate moiety into the periphery of the phenanthroline ligand does not alter the photophysical properties of the complex. In contrast, the electrochemical features of all compounds are affected upon respective functionalization compared to the reference molecule [Ru(bpy) 3 ](PF 6 ) 2 in aqueous medium. Photostability tests in water or in water/persulfate show a dependency of the stability towards photodecomposition on quenching efficiency with persulfate anion. The lower quenching efficiency thus leads to increased stability based on the negative charge of the phosphonate moiety in 2 and P1 in aqueous medium following a quenching efficiency trend of [Ru(bpy) 3 ](PF 6 ) 2 > 1 > 2 > P1. Photocatalytic water oxidation using [Ru(dpp)(pic) 2 ](PF 6 ) 2 reveals that compound 1 and [Ru(bpy) 3 ](PF 6 ) 2 doe not exhibit any activity under the utilized conditions, P1 shows a negligible TON of 7, whereas compound 2 reaches a TON of 140 after 1 h. This fact highlights that the redox potential is not the sole driver in the catalytic cycle and accentuates the importance of different criteria determining the suitability of photosensitizers in light-driven water oxidation, such as light absorption, redox potential of the Ru III /Ru II event, photostability towards and quenching efficiency with the sacrificial agent.

Ruthenium(ii) complexes with phosphonate-substituted phenanthroline ligands: synthesis, characterization and use in organic photocatalysis

“…It is also worth noting that our proton assignment of bpy ligands disagrees with the signal attribution in a series of mixed ligand complexes [Ru( phen)(bpy) 2 ] 2+ bearing 5-substituted phenanthrolines, which was reported by Ye et al 44 and Rau et al 41 and were based on only COSY measurements and common sense arguments.…”

“…cPreviously reported data for this compound (in DMF, 0.1 M Bu 4 NBF 4 , vs. Fc +/ Fc): E 1a = 0.75 V, E 1c (L 1 0/ ˙ − ) = −1.70 V, E 2c (L 2 0/ ˙ − ) = −2.00 V, E 3c (L 3 0/ ˙ − ) = −2.20. 41 …”

“…65 dPreviously reported data for this compound: λ abs ( ε × 10 −3 ) 450 (15.08), 287 (56), 265 (51) nm (M −1 cm −1 ); λ em = 601 nm. 41 e Ru-4,7Ph 2 = bis(2,2′-bipyridine)(4,7-diphenyl-1,10-phenanthroline)ruthenium( ii ) hexafluorophosphate. Taken from ref.…”

“…dPreviously reported data for this compound: λ abs ( ε × 10 −3 ) 450 (15.08), 287 (56), 265 (51) nm (M −1 cm −1 ); λ em = 601 nm. 41 …”

“…When our work was in progress, 40 the synthesis of Ru-5P and its use in water splitting were reported. 41…”