Merging of the photocatalysis and copper catalysis in metal–organic frameworks for oxidative C–C bond formation

Abstract

A new approach to merge Cu-catalysis/Ru-photocatalysis within one single MOF was achieved by incorporating [SiW11O39Ru(H2O)]5– into Cu–BPY MOFs.

Applications of inorganic‐organic hybrid architectures based on polyoxometalates in catalyzed and photocatalyzed chemical transformations

“…The combination of photoactive catalysts with the MOF metal and using the outcome, is expected to be more promising due to synergism effect. Duan and co‐workers used this approach to merge Cu‐catalysis/Ru‐photocatalysis within one single MOF by incorporation of the photoredox catalyst ruthenium (III)‐substituted [SiW 11 O 39 Ru(H 2 O)] 5– into the pores of copper (II)‐bipyridine MOFs . The resulting hybrid material (referred to as CR‐BPY1) exhibited an absorption band centered at 398 nm in the solid‐state UV‐Vis spectrum.…”

Preparation and Structural Characterization of Mono‐Ru‐Substituted α2‐Dawson‐Type Phosphotungstate with a Carbonyl Ligand and Other Ru(CO)‐Substituted Heteropolytungstates

“…photochemical reduction of carbon dioxide, [10] and photochemical oxidative C-C coupling [11] have been reported. n-.…”

“…[14] We have reported that a mono-Ru-substituted silicotungstate with an aqua ligand, [α-SiW 11 3 (acac: acetylacetonate) under hydrothermal conditions [see Equation (1)] and that it can be further converted into a carbonyl(CO)-coordinated complex, [α-SiW 11 O 39 Ru II (CO)] 6-, by increasing the reaction time [see Equation (2)]. [15] CO produced from acac ligand under the reaction conditions might react with [α-Si-W 11 The metal-carbonyl moiety M(CO) n , (M = Mn, Re, and Ir) is known to be an important component of POMs, and many POMs with M(CO) n have been prepared and characterized. [17] The CO coordinating to metals has a characteristic IR band and is a good indicator to investigate photochemically induced electron transfer from the metal to polyoxometalates.…”

A Novel Ruthenium-Decorating Polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH)2]·24H2O: An Active Heterogeneous Oxidation Catalyst for Alcohols

“…Noble metals containing polyoxometalates (POMs), in particular ruthenium (Ru)-incorporating structures [1], have been widely implemented in homo-/heterogeneous oxidation catalysis of both organic [2,3,4,5,6,7,8,9,10,11,12,13] and water-splitting reactions [14,15,16,17,18], and have therefore been attracting ever-increasing attention in recent decades. Since the discovery of the first Ru-containing POM [SiW 11 O 39 RuL] n− in 1989 [2], this domain has been further explored by the research groups of Neumann, Sadakane, Bonchio, Pope, Nomiya, Proust, Hill, Bond, Kortz, Bi and others [19].…”

“…Among them, the wholly inorganic Ru-containing POMs represent an important subclass, which had been studied previously but with only a few structures reported as compared to those with inorganic-organic hybrid Ru-containing POMs. Up until now, the majority of investigations in this area of research have been dominated by the preparations and characterizations of Ru-substituted or -sandwiched lacunary Keggin/Dawson-type heteropolytungstates [2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43], such as mono-Ru substituted polyanions [XW 11 O 39 Ru III (H 2 O)] n− (X = Si, Ge, P) [2,3,4,5,20,21,22,23,24,25] and [P 2 W 17 O 61 Ru III (H 2 O)] 5− [26,27,28], di-Ru-sandwiched/substituted polyanions {O[Ru IV (X)P 2 W 17 O 61 ] 2 } 16− (X = OH, Cl) [27], {[(XZnRu 2 III (OH)(H 2 O)](ZnW 9 O 34 ) 2 } n− (X = W, Zn) [29,30,…”