3d-4f heterometallic cluster incorporated polyoxoniobates with magnetic property

A series of 3d-4f heterometallic cluster incorporated polyoxoniobates (PONbs) with different magnetic properties were first made and characterized. This work not only provides a promising strategy to make new heterometallic...

Stabilizing a metalloid {Zn12} unit within a polymetallide environment in [K2Zn20Bi16]6−

The access to molecules comprising direct Zn–Zn bonds has become very topical in recent years for various reasons. Low-valent organozinc compounds show remarkable reactivities, and larger Zn–Zn-bonded gas-phase species exhibit a very unusual coexistence of insulating and metallic properties. However, as Zn atoms do not show a high tendency to form clusters in condensed phases, synthetic approaches for generating purely inorganic metalloid Znx units under ambient conditions have been lacking so far. Here we show that the reaction of a highly reductive solid with the nominal composition K5Ga2Bi4 with ZnPh2 at room temperature yields the heterometallic cluster anion [K2Zn20Bi16]6–. A 24-atom polymetallide ring embeds a metalloid {Zn12} unit. Density functional theory calculations reveal multicenter bonding, an essentially zero-valent situation in the cluster center, and weak aromaticity. The heterometallic character, the notable electron-delocalization, and the uncommon nano-architecture points at a high potential for nano-heterocatalysis.

Integration of Bio-inspired lanthanide-transition metal cluster and P-doped carbon nitride for efficient photocatalytic overall water splitting

Photosynthesis in nature uses the Mn4CaO5 cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II (PS II). Herein, we demonstrate a bio-inspired heterometallic cluster LnCo3 (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of CaMn4O5 cluster. Anchoring LnCo3 on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo3/PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption (TA) spectroscopy revealed the transfer of photoexcited electron and hole into the PCN and LnCo3 for hydrogen and oxygen evolution reactions, respectively. DFT calculation showed the cooperative water activation on lanthanide and O-O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting.