Chirality meets visible-light photocatalysis in a molecular cerium vanadium oxide cluster

Abstract

The first example of a molecular cerium vanadium oxide photocatalyst is presented. A cerium vanadium oxide cluster, (nBu 4 N) 2 - [(Ce(dmso)

Beyond Charge Balance: Counter‐Cations in Polyoxometalate Chemistry

“… Structural representation of the cation‐stabilized POMs {Bi 6 Fe 13 } , {Bi 4 V 13 }, and {Ce 2 V 12 } described in Section 2.1; {Ce 2 V 12 } =[(Ce(dmso) 3 ) 2 V IV V V 11 O 33 Cl] 2− …”

Jenseits von Ladungsausgleich: Gegenkationen in der Polyoxometallat‐Chemie

“… Strukturdarstellung der kationenstabilisierten POMs {Bi 6 Fe 13 } , {Bi 4 V 13 } und {Ce 2 V 12 } , beschrieben in Abschnitt 2.1; {Ce 2 V 12 } =[(Ce(dmso) 3 ) 2 V IV V V 11 O 33 Cl] 2− …”

“…Dies zeigt, dass die Stabilisierung von POM‐Clustern durch große Metallkationen von breiter Bedeutung für die POM‐Chemie sein könnte. Weitere Belege hierfür liefern kürzlich veröffentlichte Studien, die neuartige Vanadatcluster durch Koordination von Ce 3+ ‐Kationen an freie Bindungsstellen demonstrieren . Zum Schluss sei angemerkt, dass sowohl {Bi 6 Fe 13 } als auch {La 4 Mo 12 } Metall‐Oxo‐Kationen darstellen – wir werden auf diese Verbindungsklasse in Abschnitt 4 zurückkommen.…”

Photocatalytic reactivity tuning by heterometal and addenda metal variation in Lindqvist polyoxometalates

“…6,7 This approach can also be extended to the development of POM photocatalysts, 14,15 as the electronic properties of the clusters (and therefore their visible-light photoactivity) are controlled by the underlying cluster structure. [21][22][23][24][25][26] Based on this concept, functionalization routes were developed where selective metal substitution is used to photosensitize clusters in the visible region. 23,24,26,27 Thus far, the concept of metal-substituted POM photocatalysts has mainly been focused on Keggin derivatives [XM 12 O 40 ] n− (M = V, Mo, W) 28,29 whereas the development of other heterometallic, photoactive POM clusters is still in its infancy.…”

“…[21][22][23][24][25][26] Based on this concept, functionalization routes were developed where selective metal substitution is used to photosensitize clusters in the visible region. 23,24,26,27 Thus far, the concept of metal-substituted POM photocatalysts has mainly been focused on Keggin derivatives [XM 12 O 40 ] n− (M = V, Mo, W) 28,29 whereas the development of other heterometallic, photoactive POM clusters is still in its infancy. 30,31 Based on this background, we started to investigate small prototype clusters 24 where selective metal exchange can be used to tune the electronic cluster properties whilst retaining the physical cluster architecture.…”