The only feasible access to non‐face‐centered cubic (FCC) copper was by physical vapor deposition under high vacuum. Now, non‐FCC copper is observed in a series of alkynyl‐protected Cu53 nanoclusters (NCs) obtained from solution‐phase synthesis. Determined by single‐crystal X‐ray crystallography, the structures of Cu53(C≡CPhPh)9(dppp)6Cl3(NO3)9 and its two derivatives reveal an ABABC stacking sequence involving 41 Cu atoms. It can be regarded as a mixed FCC and HCP structure, which gives strong evidence that Cu can be arranged in non‐FCC lattice at ambient conditions when proper ligands are provided. Characterization methods including X‐ray absorption fine structure, XPS, ESI‐MS, UV/Vis, Auger spectroscopy, and DFT calculations were carried out. CuII was shown to successively coordinate with introduced ligands and changed to CuI after bonding with phosphine. The following addition of NaBH4 and the aging step further reduced it to the Cu53 NC.

Photochemical methods are effective for controllable synthesis of silver nanoparticles with specific sizes and shapes. Whether they are capable of fabricating Ag nanoclusters (NCs) with atomic precision is yet to be proved. In this work, we synthesize an atomically precise Ag NC, [Ag 25 (4-MePhC�C) 20 (Dpppe) 3 ](SbF 6 ) 3 (Ag 25 ), via a process mediated by visible light. Its total structure is determined by X-ray crystallography. The investigation of the mechanism reveals that the formation of Ag 25 is triggered by a photoinduced electron-transfer (PET) process. An electron of certain amines is excited by light with wavelength shorter than 455 nm and transferred to Ag + . The amine is oxidized to the corresponding amine N-oxide. Such a PET process is supported by experimental and density functional theory studies. To expand the application scope of the photochemical method, another three NCs, [Ag 19 (4-t BuPhC� C) 14 (Dpppe) 3 ](SbF 6 ) 3 (Ag 19 ), [Ag 32 (4-t BuPhC�C) 22 (Dppp) 4 ](SbF 6 ) 3 (Ag 32 ), and bimetallic [Ag 22 Au 3 (4-t BuPhC�C) 20 (Dpppe) 3 ](SbF 6 ) 3 (Ag 22 Au 3 ), are produced by replacing certain ingredients. Furthermore, since the formation of Ag 19 can be regarded as a photochromatic process, a facile amine visual detection method is also presented based on this mechanism.

Graphitic carbon nitride (g-C 3 N 4 ) is an organic semiconductor for photocatalysis. However, it still suffers from low surface area and rapid e − / h + recombination, which limits its further activity enhancement. In this work, an atomically precise alkynyl-and phosphine-protected Ag 33 (4-MePhC� C) 22 (Dppp) 4 nanocluster is synthesized. It is facilely loaded onto g-C 3 N 4 nanosheets by a one-step process. The resulting Ag 33 /g-C 3 N 4 nanocomposite is thoroughly characterized. Its activity is evaluated in the photodegradation of methyl orange. Ag 33 /g-C 3 N 4 has shown a 16-fold activity enhancement compared to pristine g-C 3 N 4 . The mechanism investigation using UV−vis/ diffuse-reflectance spectroscopy spectra, photocurrent response, and Nyquist plots has revealed the origin of this superior performance.

Purple of Cassius is a pigment based on gold colloid known since ancient time. It had a profound influence on the modern nanoscience. But the origin of the small size...

A close-packed superstructure consisting of Ti12 and Ti6 in one single crystal is prepared via solvothermal synthesis. The closest twelve neighboring Ti6 clusters form a distorted cuboctahedron centered with a...