Layered and three-dimensional uranyl–organic assemblies with 4,4′-oxidiphthalic acid

Hydrothermal reactions of uranyl nitrate and 4,4＇-oxidiphthalic acid（H4L） resulted in the formation of three new uranyl-organic framework materials,namely（NH4）2[（UO2）3（L）2]·5H2O（1）,（NEt4）[（UO2）3（H2O）（L）（HL）]（2） and（UO2）7（H2O）2（phen）4（L）2（HL）2（3）（NEt4 = tetraethylammonium,phen = 1,10-phenanthroline）.These three structures all comprise common uranyl pentagonal bipyramids.In 1,UO7polyhedra are linked by hexadentate ligands to form a 3D framework with 1D channels,in which are located NH4^＋ ions and water molecules.While in 2,the organic ligands adopt pentadentate and hexadentate coordination modes,ligating UO7 units to create a layered structure with channels filled by NEt4^＋ ions.For 3,uranyl square bipyramids are also accommodated together with pentagonal bipyramids,which are linked by tetradentate carboxylate ligands to produce the layered assembly.Phen molecules also coordinate to the uranyl centers to build up the structure.Luminescent studies indicate that 2 and 3 exhibit the characteristic uranyl emission.

Organic dye assemblies with aggregation-induced photophysical changes and their bio-applications

Phototheranostics provide a safe,effective,and noninvasive way for the diagnosis and treatment of contemporary diseases,and organic dyes play a vital role.For example,chemical modification endowed dyes with powerful reactive oxygen species or heat generation ability,favoring for photodynamic therapy and photoacoustic(PA)imaging guided photothermal therapy(PTT)of serious diseases.Therefore,photophysical properties manipulation of dyes has become the focus in current dye chemistry research.The development of aggregate science has made great effort to solve this problem.In recent years,a large number of studies have focused on molecular aggregation behavior and its effect on photophysical performance.The most famous example is the discovery of aggregation-induced emission(AIE)phenomenon.Based on AIE theory,more theories for revealing the relationship between molecular aggregation behavior and photophysical properties were proposed and elucidated.The photophysical property changes caused by dye aggregation have become a unique discipline,guiding the development of molecular science and material science.With the help of molecular self-assembly,controllable aggregation of dyes can be realized,and stable nano-theranostic reagents can be obtained.Furthermore,constructing dye assemblies with various photophysical properties will greatly reduce the cost of theranostic reagents,thus,expanding biomedical applications of organic dyes.Therefore,this review focuses on the photophysical characteristic changes caused by dye aggregation and their biological applications including,fluorescence/phosphorescence/PA imaging as well as photodynamic and PTT.This review will provide guidance for the design of organic dyes,the development of controllable aggregation methods,and the construction of multifunctional phototheranostic reagents.

Helical supramolecular nanorods via sequential meticulous tailoring of noncovalent interaction and light irradiation

Polymers are widely recognized to entail random conformations in good solvent governed by the need for achieving the highest entropy to reach thermodynamic equilibrium.In this context,it remains grand challenging to directly arrange them into ordered conformation as building blocks for further self-assembling into hierarchal structures.Herein,we report a simple yet viable strategy to progressively assemble rationally designed azobenzene-containing alternating copolymer(i.e.,poly(binaphthylspacer-azobenzene-alt-hexaethylene glycol),denoting P(BNPSAzo-alt-EG_(6))_(24))into helical supramolecular nanorods.Specifically,P(BNPSAzo-alt-EG_(6))_(24) chains in good solvent are firstly self-assembled into helical single molecular micelles in good solvent via intramolecular π-π interaction between binaphthyl groups as well as between azobenzene moieties.Subsequently,by simply introducing water into the solution that is allowed to dwell for a certain period of time,single molecular micelles are selfassembled into well-defined vesicles.Finally,these isotropic vesicles could be further transformed into anisotropic helical supramolecular nanorods with enhanced aggregate-induced emission(AIE)capability driven by repeated,light-triggered cistrans isomerization of azobenzene moieties with the retention of π-π interacted binaphthyl groups.This study highlights a facile route to yielding morphology-rich,functional assemblies from a single polymer via judiciously exploiting non-covalent interaction and light of different wavelength as highly effective trigger in a non-invasive manner for potential applications in controlled release and fluorescent labelling.

The role of halogen bonding in improving OFET performance of a naphthalenediimide derivative

Controlling microstructure and thin film morphology of organic semiconductors by supramolecular arrangement is critical to improving their device performance. To realize well-controlling supramolecular assembly, a core-expanded naphthalene diimides derivative （1） was designed and synthesized as an n-type organic semiconductor and also as a halogen bonding （XB） donor that could form complementary XBs with 2,2-dipyridine or 2,2-bipyrimidine acceptor. The XB interactions in the solid state of 1/2,2- dipyridine and 1/2,2-bipyrimidine were confirmed by a series of characterization methods, such as thermal gravimetric analysis （TGA）, X-ray photoelectron spectroscopy （XPS）, nuclear magnetic resonance （NMR） involving 13F NMR and solid-state 13C NMR. Organic field-effect transistors （OFETs） based on XB complexes 1/2,2-dipyridine or 1/2,2-bipyrimidine showed better device performance than that of devices based on pure 1, with the average electron mobility increased more than doubled （from 0.027cm2V-1 s-1 to 0.070cm2V-1 s-1）.