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Economic reform in China has

Understanding the origin and structural basis of the photoluminescence (PL) phenomenon in thiolate-protected metal nanoclusters is of paramount importance for both fundamental science and practical applications. It still remains a...

Molecular stacking modes, generally classified as H-, J-, and X-aggregation, play a key role in determining the optoelectronic properties of organic crystals. However, the control of stacking transformation of a specific molecule is an unmet challenge, and a priori prediction of the performance in different stacking modes is extraordinarily difficult to achieve. In particular, the existence of hybrid stacking modes and their combined effect on physicochemical properties of molecular crystals are not fully understood. Herein, unexpected stacking transformation from H- to J- and X-aggregation is observed in the crystal structure of a small heterocyclic molecule, 4,4′-bipyridine (4,4′-Bpy), upon coassembly with N -acetyl- l -alanine (AcA), a nonaromatic amino acid derivative. This structural transformation into hybrid stacking mode improves physicochemical properties of the cocrystals, including a large red-shifted emission, enhanced supramolecular chirality, improved thermal stability, and higher mechanical properties. While a single crystal of 4,4′-Bpy shows good optical waveguiding and piezoelectric properties due to the uniform elongated needles and low symmetry of crystal packing, the significantly lower band gap and resistance of the cocrystal indicate improved conductivity. This study not only demonstrates cocrystallization-induced packing transformation between H-, J-, and X-aggregations in the solid state, leading to tunable mechanical and optoelectronic properties, but also will inspire future molecular design of organic functional materials by the coassembly strategy.

Metal-organic frameworks (MOFs), a class of microporous crystalline materials composed of organic linkers and inorganic metal ions, have attracted increasing attention in recent years. [1] Owing to their flexible tunability in composition and structure, MOFs have been applied in many areas, especially, catalysis. [2] For application of traditional MOFs in In recent years, metal-organic frameworks (MOFs) have received extensive interest because of the diversity of their composition, structure, and function. To promote the MOFs' function and performance, the construction of hollow structural metal-organic frameworks and nanoparticle-MOF composites is significantly effective but remains a considerable challenge. In this article, a transformation strategy is developed to synthesize hollow structural Co-MOF-74 by solvothermal transformation of ZIF-67. These Co-MOF-74 particles exhibit a double-layer hollow shell structure without remarkable shape change compared to original ZIF-67 particles. The formation of hollow structure stemmed from the density difference of Co between ZIF-67 and Co-MOF-74. By this strategy, hollow structural Co-MOF-74 with different sizes and shapes are obtained from corresponding ZIF-67, and metal nanoparticles@Co-MOF-74 is synthesized by corresponding nanoparticles@Co-ZIF-67. To verify the structural advantages of hollow structural Co-MOF-74 and Ag nanoparticles@Co-MOF-74, photocatalytic CO 2 reduction is used as a model reaction. Conventionally synthesized Co-MOF-74 (MOF-74-C), hollow structural Co-MOF-74 synthesized by transformation method (MOF-74-T) and Ag nanoparticles@ Co-MOF-74 (AgNPs@MOF-74) are used as cocatalysts in this reaction. As a result, the cocatalytic activity of MOF-74-T and AgNPs@MOF-74 is 1.8 times and 3.8 times that of MOF-74-C, respectively.