Near-Infrared-II Photoactivated Iron(III) Complexes for Highly Efficient RNS and ROS Synergistic Therapy.

Reactive nitrogen species (RNS) are more lethal than reactive oxygen species (ROS), which gives them a very promising future in the field of cancer treatment. However, there are still a few drugs available for RNS generation. In this work, two 5th-order nonlinear optical materials, FB-Fe(III)/SNP@PEG and FB-Fe(II)-FB/SNP@PEG, are synthesized.

Dual-quartet phosphorescent emission in the open-shell MAg (M = Pt, Pd) nanoclusters.

Dual emission (DE) in nanoclusters (NCs) is considerably significant in the research and application of ratiometric sensing, bioimaging, and novel optoelectronic devices. Exploring the DE mechanism in open-shell NCs with doublet or quartet emissions remains challenging because synthesizing open-shell NCs is difficult due to their inherent instability. Here, we synthesize two dual-emissive MAg(PFBT)(TPP) (M = Pt, Pd; PFBT = pentafluorobenzenethiol; TPP = triphenylphosphine) NCs with a 7-electron open-shell configuration to reveal the DE mechanism.

A bimetallic AgCu(S--CH)(CHCOO) nanocluster featuring an irregular Ag kernel.

Here, we report the synthesis and atomic structure of a AgCu(SR)(CHCOO)·(CH) nanocluster (AgCu for short, SR denotes cyclohexanethiol), confirmed by single-crystal X-ray diffraction (SC-XRD), electrospray ionization mass spectrometry (ESI-MS), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). X-ray crystallographic analysis revealed that AgCu consisted of an irregular Ag core, stabilized by the AgCu(SR)(CHCOO) shell. The shell consisted of two nearly planar Cu(SR) moieties, three monomeric [-SR-Ag-SR-] units and three Cu(CHCOO) staples.

Interdependence between nanoclusters AuAg and AuAg.

Whole series of nanoparticles have now been reported, but probing the competing or coexisting effects in their synthesis and growth remains challenging. Here, we report a bi-nanocluster system comprising two ultra-small, atomically precise nanoclusters, AuAg(SR) and AuAg(SR)(Dppm) (SR = cyclohexyl mercaptan, Dppm = bis(diphenylphosphino)-methane). The mechanism by which these two nanoclusters coexist is elucidated, and found to entail formation of the unstable AuAg(SR), followed by its partial conversion to AuAg(SR)(Dppm) in the presence of di-phosphorus ligands, and an interdependent bi-nanocluster system is established, wherein the two oppositely charged nanoclusters protect each other from decomposition.

Metal synergistic effect on cluster optical properties: based on Ag series nanoclusters.

Due to their high biological stability and strong fluorescence, thiolated metal nanoclusters have shown great potential as a new generation of bio-nano-materials. However, the ambiguous mechanism of fluorescence impedes the design and synthesis of highly fluorescent nanoclusters. In this work, Ag nanocluster and its dopants were chosen as a model to study the effect of metal synergy on the optical properties.

Isomerism in Au-Ag Alloy Nanoclusters: Structure Determination and Enantioseparation of [AuAg(SR)(dppm)X].

Revealing structural isomerism in a nanocluster remains significant but challenging. Herein, we have obtained a pair of structural isomers, [AuAg(SR)(dppm)X]-C and [AuAg(SR)(dppm)X]-Ac [dppm = bis(diphenyphosphino)methane; HSR = 1-adamantanethiol/ tert-butylmercaptan; X = Br/Cl; C stands for one of the structural isomers being chiral; Ac stands for another being achiral], that show different structures as well as different chiralities. These structures are determined by single-crystal X-ray diffraction and further confirmed by high-resolution electrospray ionization mass spectrometry.

Aggregation-Induced Emission (AIE) in Ag-Au Bimetallic Nanocluster.

Herein we report the synthesis and structure determination of a non-fluorescent Au Ag (dppm) (SAdm) (BPh ) (dppm=bis(diphenylphosphino)methane and HSAdm=1-adamantane mercaptan) nanocluster in methanol with extremely strong AIE when aggregating to the solid state (i.e., film or crystal).

Highly Branched Polymers with Layered Structures that Mimic Light-Harvesting Processes.

Hyperbranched polymers (HBPs) with decorated donor and acceptor chromophores in different domains were constructed to demonstrate the function of light harvesting in a polymeric nanostructure. Taking advantage of our recently developed chain-growth copper-catalyzed azide-alkyne cycloaddition polymerization, two structural parameters in the HBPs, for example, the molar ratio of the acceptor Coumarin 343 in the core to the donor Coumarin 2 on the periphery, and the average distance between these two layers, could be independently varied in a one-pot synthesis. The results demonstrated an efficient energy transfer from the excited Coumarin 2 to the ground-state Coumarin 343 in the core, with the efficiency of the energy transfer reaching as high as 98 %.

Thiol-Induced Synthesis of Phosphine-Protected Gold Nanoclusters with Atomic Precision and Controlling the Structure by Ligand/Metal Engineering.

Efficient synthesis of atomically precise phosphine-capped gold nanocluster (with >10 metal atoms) is important to deeply understand the relationship between structure and properties. Herein, we successfully utilize the thiol-induced synthesis method and obtain three atomically precise phosphine-protected gold nanoclusters. Single-crystal X-ray structural analysis reveals that the nanoclusters are formulated as [Au(Dppm)](BPh), [Au(Dppm)Br](BPh), and [Au(Dppm)(CN)] (where Dppm stands for bis(diphenylphosphino)methane), which are further confirmed by electrospray ionization mass spectrometry, thermogravimetric analysis, and X-ray photoelectron spectroscopy.

Preparation of hyperstar polymers with encapsulated Au(SR) clusters as recyclable catalysts for nitrophenol reduction.

A robust approach is developed to prepare hyperstar polymer-Au(SR) nanocomposites for catalysis. The synthesis started with atom transfer radical copolymerization of an inimer with a cyclic disulfide-containing methacrylate monomer in a microemulsion to produce hyperbranched copolymers with high molar mass, low polydispersity, and a vital fraction of dangling disulfide groups. The core-shell structured hyperstar polymers were then prepared using hyperbranched copolymers as macroinitiators to polymerize oligo(ethylene glycol) methyl ether methacrylate (M = 500) and grow the radiating arms.

Crystal structure of Au₂₅(SePh)₁₈ nanoclusters and insights into their electronic, optical and catalytic properties.

The crystal structure of selenolate-capped Au25(SePh)18(-) nanoclusters has been unambiguously determined for the first time, and provides a solid basis for a deeper understanding of the structure-property relationships. The selenolate-capped Au25 cluster shows noticeable differences from the previously reported Au25(SCH2CH2Ph)18(-) counterpart, albeit both share the icosahedral Au13 core and semi-ring Au2(SeR)3 or Au2(SR)3 motifs. Distinct differences in the electronic structure and optical, catalytic and electrochemical properties are revealed by the coupling experiments with density functional theory (TD-DFT) calculations.