Optothermally Programmable Liquids with Spatiotemporal Precision and Functional Complexity.

Due to the intrinsic lack of spatial order and self-supported shape, liquids are often incompatible with precision manufacturing/processing and are potentially limited for advanced functionality. Herein, an optothermal strategy is developed to fully command phase-separated liquids with unprecedented spatiotemporal addressability. Specifically, a laser is focused onto an Au film to create a hot spot that locally demixes a temperature-responsive solution to produce a single optothermal droplet.

Large-Scale Structural Refinement and Screening of Zirconium Metal-Organic Frameworks for HS/CH Separation.

Zirconium-based metal-organic frameworks (Zr-MOFs) with Zr inner cores represent a subfamily of nanoporous materials with good physicochemical stabilities, showing significant prospect for practical applications in various fields. Although computational characterization can play an important role that is complementary to experimental efforts, the availability of chemically realistic Zr-MOF structures is one of the prerequisites to accurately evaluate their performance as well as provide valuable insights for guiding material design. In this work, periodic density functional theory (DFT) calculations combined with a molecular mechanics method were performed to optimize the crystalline structures of over 182 experimentally synthesized Zr-MOFs that contain no less than 10-coordinated ZrO nodes, leading to a database consisting of the structures having a diversity of topologies, pore sizes, and functionalities.

A new type of halogen bond involving multivalent astatine: an ab initio study.

Theoretical studies on the dimers formed by CO with the halides of multivalent astatine as a Lewis-acid center are carried out to examine the typical characteristics of supervalent halogen bonds. Calculations at the MP2/aug-cc-pVTZ level reveal that the multiple nucleophilic sites of multivalent halide monomers can promote the formation of various types of halogen bonds, among which the most stable ones are At-halogen bond complexes with multivalent astatine as a Lewis acid center, followed by the π-halogen bond dimers, and the weakest ones are the X-halogen bonds. Compared with multivalent Cl-, Br-, and I-centers, At, as the heaviest halogen, exhibits the highest halogen-bond donating ability.

A theoretical investigation on Cu/Ag/Au bonding in XHP⋯MY(X = H, CH, F, CN, NO; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes.

Intermolecular interaction of XHP···MY (X = H, CH, F, CN, NO; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes was investigated by means of an method. The molecular interaction energies are in the order Ag < Cu < Au and increased with the decrease of R. Interaction energies are strengthened when electron-donating substituents X connected to XHP, while electron-withdrawing substituents produce the opposite effect.