Although progress has been made to improve photocatalytic CO2 reduction under visible light (λ>400 nm), the development of photocatalysts that can work under a longer wavelength (λ>600 nm) remains a challenge. Now, a heterogeneous photocatalyst system consisting of a ruthenium complex and a monolayer nickel‐alumina layered double hydroxide (NiAl‐LDH), which act as light‐harvesting and catalytic units for selective photoreduction of CO2 and H2O into CH4 and CO under irradiation with λ>400 nm. By precisely tuning the irradiation wavelength, the selectivity of CH4 can be improved to 70.3 %, and the H2 evolution reaction can be completely suppressed under irradiation with λ>600 nm. The photogenerated electrons matching the energy levels of photosensitizer and m‐NiAl‐LDH only localized at the defect state, providing a driving force of 0.313 eV to overcome the Gibbs free energy barrier of CO2 reduction to CH4 (0.127 eV), rather than that for H2 evolution (0.425 eV).

Owing to the atomically precise structures, metal nanoclusters (NCs) have always served as model molecular tools to analyze NC surface chemistry and to investigate structure−property correlations. Herein, a series of bis‐N‐heterocyclic carbene (NHC)‐protected NCs of type [Au11(bis‐NHC)5]3+ and [Au13(bis‐NHC)5Br2]3+ obtained from direct reduction of Au−bis‐NHC complexes are described. The NCs type obtained depends on the N‐wingtip substituents of the Au−bis‐NHC complexes. Subtle changes in the lengths of the N‐wingtip substituents enable the fine‐tuning of the kernel with either Au11 or Au13 clusters. Among them, [Au11(bis‐NHC)5]3+ cluster is the first homoleptic NHC‐stabilized Au NC. The composition and structures of these NCs are unequivocally determined by single crystal X‐ray crystallography and electrospray ionization mass spectrometry. Contrary to the non‐emissive Au11 cluster, the Au13 NC exhibits high emission in solution and the luminescence properties are severely dependent onto the substituent effects. Additionally, peculiar Au⋯HC interactions are present in NHC‐protected clusters.

Recent progress on the synthetic methods, structural features, and promising applications of NHCs and their precursors in functionalised porous materials is summarised.

The properties of supramolecular structures are highly dependent on their metal-centered building blocks and organic linkers, thus the search for novel systems will lead to new functions and applications for these unique assemblies. Here, two discrete triangular trimetallic sandwich building blocks were developed to construct supramolecular assemblies through coordination-driven self-assembly with organosulfur ligands. A series of tubelike (Tr 2 Pd 3 ) 4 L 6 assemblies (Tr = cycloheptatrienyl ring) were obtained from a discrete triangular tripalladium sandwich complex with bifunctional organosulfur ligands. By replacing the metal centers of the platinum analogue, the self-assembly process resulted in the clean formation of (Tr 2 Pt 3 ) 2 L 3 triple helicates instead of tubelike species. The trimetallic sandwich building blocks were also shown to form face-capped (Tr 2 M 3 ) 4 L 4 (M = Pd or Pt) tetrahedral cages when trifunctional organosulfur ligands were used. The supramolecular assemblies were comprehensively analyzed by X-ray crystallography. A metal-cluster-induced structural transformation between (Tr 2 Pd 3 ) 4 L 4 tubes and (Tr 2 Pt 3 ) 2 L 3 triple helicates was observed. Furthermore, the face-capped (Tr 2 Pd 3 ) 4 L 4 cage possesses a tetrahedral cavity allowing the encapsulation of a series of guests.

Reduction of photocatalytic CO 2 into renewable hydrocarbon solar fuels is considered to be a promising strategy that can simultaneously address global energy needs as well as environmental concerns. To date, making use of a higher wavelength for photocatalytic conversion of CO 2 to CH 4 continues to be highly challenging. In this work, we report a highly selective reduction of CO 2 into CH 4 and CO by introducing Ni species into CoFe-layered double hydroxide (LDH) as the visible light photocatalyst in conjunction with a Ru complex sensitizer. A more interesting finding is that the selectivity of CH 4 was raised to 78.9% as compared to 0% of CoFe-LDH, while the H 2 evolution was suppressed to 1.7% as compared to 30.5% of CoFe-LDH under light irradiation at λ > 500 nm. The involvement of Ni 2+ ions in the CoFe-LDH layers has shown to promote the photoinduced electron−hole pair separation and thereby facilitate the photocatalytic efficiency. This work provides a new strategy for exploring the Ni-based earth-abundant photocatalysts for CO 2 photoreduction.