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The stable cross-shaped CsPbI

In recent times, mixed cation-based perovskite has gained a lot of popularity in high-performance solar cells. However, the mixed cations based on the FAxMA1–xPbI3 absorber layer still exhibit a hi...

Polymer electrolytes (PEs) have attracted tremendous research interest for their potential to offer improved safety and energy capacity in next-generation battery technologies. Among the different classes of PEs, single-ion conductors (SICs) are particularly interesting due to their high transference numbers. Nevertheless, a detailed understanding of how molecular structure impacts the properties of SIC-PEs is absent, limiting the ability to design improved materials. Here, we present the synthesis and characterization of a new class (seven examples provided) of polyanions featuring fluorinated aryl sulfonimide tagged (FAST) anions as side chains. These "polyFAST"salts are shown to outperform the widely used poly[(4-styrenesulfonyl) (trifluoromethanesulfonyl)imide] due to their strongly electron-withdrawing side chains and enhanced distance between anionic sites, providing higher electronic conductivities at all salt concentrations and in some cases superior electrochemical oxidative stability. Moreover, they provide a platform for discovery of fundamental relationships between macromolecular composition, as programmed through monomer structure, and SIC-PE bulk properties. Finally, we leverage the electron-deficient nature of polyFAST salts to demonstrate a new poly(solvate ionic liquid) (polySIL) concept that offers a promising pathway toward high-performance PEO-free SIC-PEs.

Molecular details often dictate the macroscopic properties of materials, yet due to their vastly different length scales, relationships between molecular structure and bulk properties can be difficult to predict a priori, requiring Edisonian optimizations and preventing rational design. Here, we introduce an easy-to-execute strategy based on linear free energy relationships (LFERs) that enables quantitative correlation and prediction of how molecular modifications, i.e., substituents, impact the ensemble properties of materials. First, we developed substituent parameters based on inexpensive, DFT-computed energetics of elementary pairwise interactions between a given substituent and other constant components of the material. These substituent parameters were then used as inputs to regression analyses of experimentally measured bulk properties, generating a predictive statistical model. We applied this approach to a widely studied class of electrolyte materials: oligo-ethylene glycol (OEG)–LiTFSI mixtures; the resulting model enables elucidation of fundamental physical principles that govern the properties of these electrolytes and also enables prediction of the properties of novel, improved OEG–LiTFSI-based electrolytes. The framework presented here for using context-specific substituent parameters will potentially enhance the throughput of screening new molecular designs for next-generation energy storage devices and other materials-oriented contexts where classical substituent parameters (e.g., Hammett parameters) may not be available or effective., Parameterizing organic substituents: Chemical structures are quantitatively connected to Li+ conductivity and viscosity in a statistical model that allows for prediction of new electrolyte materials.

CsPbCl3:Mn2+ is a practical solution for obtaining red-orange light inorganic perovskite nanocrystals since CsPbI3 is unstable. Increasing the concentration of Mn2+ is an effective way to enhance the orange-red emission of CsPbCl3:Mn2+. However, the relationship between emission intensity of the Mn2+ dopant and the concentration of Mn2+ is very chaotic in different studies. As a transition metal ion, the electronic states of Mn2+ are very sensitive to the crystal field environment. Here, the crystal field of the CsPbCl3:Mn2+ nanocrystals was adjusted by co-doping other cations, and the concentration of Mn2+ remained unchanged. Additionally, the crystal field strength of different samples was calculated. Compared with the CsPbCl3:Mn2+ nanocrystals, the red-orange peak in the fluorescence spectrum of CsPbCl3:Mn2+, Er3+ nanocrystals was redshifted from 580 to 600 nm and enhanced by 100 times successfully. The same experiment was carried out on CsPbCl3:Mn2+ nanoplatelets at the same time to confirm the changed crystal field around Mn2+. The effect of co-doping cations on the luminescence properties of Mn2+ is similar to that in nanocubes, and the mechanism was analyzed in detail.

Sequence-controlled supramolecular polymers offer new design paradigms for generating stimuli-responsive macromolecules with enhanced functionalities. The dynamic character of supramolecular links present challenges to sequence definition in extended supramolecular macromolecules, and design principles remain nascent. Here, we demonstrate the first example of using stoichiometry-control to specify the monomer sequence in a linear supramolecular polymer by synthesizing both a homopolymer and an alternating copolymer from the same glycol-substituted cyanostar macrocycle and phenylene-linked diphosphate monomers. A 2:1 stoichiometry between macrocycle and diphosphate produces a supramolecular homopolymer of general formula (A)n comprised of repeating units of cyanostar-stabilized phosphate-phosphate dimers. Using a 1:1 stoichiometry, an alternating (AB)n structure is produced with half the phosphate dimers now stabilized by the additional counter cations that emerge hierarchically after forming the stronger cyanostar-stabilized phosphate dimers. These new polymer materials and binding motifs are sufficient to bear normal and shear stress to promote significant and tunable adhesive properties. The homopolymer (A)n, consisting of cyanostar-stabilized anti-electrostatic linkages, shows adhesion strength comparable to commercial superglue formulations based on polycyanoacrylate but is thermally reversible. Unexpectedly, and despite including traditional ionic linkages, the alternating copolymer (AB)n shows weaker adhesion strength more similar to commercial white glue based on poly(vinyl acetate). Thus, the adhesion properties can be tuned over a wide range by simply controlling the stoichiometric ratio of monomers. This study offers new insight into supramolecular polymers composed of custom-designed anion and receptor monomers and demonstrates the utility of emerging functional materials based on anion-anion linkages.

Phosphorescent organic light-emitting diodes (PhOLEDs) are a kind of highly efficient and solution-processable devices for displays and light sources, which employ phosphorescent material as the gu...

Molecular details often dictate the macroscopic properties of materials, yet, due to their vastly different length scales, relationships between molecular structure and bulk properties are often difficult to predict a priori, requiring Edisonian optimizations and preventing rational design. Here, we introduce an easy-to-execute strategy based on linear free energy relationships (LFERs) that enables quantitative correlation and prediction of how molecular modifications, i.e., substituents, impact the ensemble properties of materials. First, we developed substituent parameters based on inexpensive, DFT-computed energetics of elementary pairwise interactions between a given substituent and other constant components of the material. These substituent parameters were then used as inputs to regression analyses of experimentally measured bulk properties, generating a predictive statistical model. We applied this approach to a widely studied class of electrolyte materials: oligo-ethylene glycol (OEG)-LiTFSI mixtures; the resulting model enables elucidation of fundamental physical principles that govern the properties of these electrolytes and also enables prediction of the properties of novel, improved OEG-LiTFSI-based electrolytes. The framework presented here for using context-specific substituent parameters will potentially enhance the throughput of screening new molecular designs for next-generation energy storage devices and other materials-oriented contexts where classical substituent parameters (e.g., Hammett parameters) may not be available or effective.

The power conversion efficiencies (PCEs) of potential polymer solar cells have been shown to rapidly exceed 15%. However, these high-performance devices are based on halogenated solvents that pose a significant hazard to the atmospheric environment and human beings. The use of nonhalogenated solvents makes the device less efficient because of its solubility issues. In this work, we report high-efficiency devices utilizing PffBT4T-2OD and [6,6]-phenyl C71 butyric acid methyl ester system from nonhalogenated solvents such as o-xylene (o-XY) and 1-methylnaphthalene (Me) hydrocarbon solvent. When Me was used as the additive, the PCE of prepared devices improved from 1.83 to 10.13%, which is rather higher than that of the devices processed with traditional solvents combined with chlorobenzene and 1,8-diiodooctane (8.18%). Both atomic force microscopy and transmission electron microscopy confirmed that after nonhalogen solvents are treated, a more finely phase-separated dense morphology of active layers than af...

CsPbX3 (X = Cl, Br, I) perovskite nanocrystals (NCs) are promising materials due to their excellent optoelectronic properties. In this work, we show a successful partial and reversible cation exchange reaction between Pb and Mn in both CsPbCl3 NCs and CsMnCl3 NCs systems to yield luminescent CsPb1–xMnxCl3 NCs. By adjusting the reaction time, the photoluminescence from the exciton emission of CsPbCl3 and the electron transition of Mn2+ can be tuned gradually. This work highlights the feasibility of a postsynthetic interconversion of Pb2+ and Mn2+ in cesium lead chloride perovskite nanocrystals, which enables a new strategy to reduce the toxicity and adjust the emissions of CsPbCl3 NCs. In the end, we also discuss the plausible mechanisms for cation exchange in perovskite materials.

Fluorescence is critical to many advanced materials including OLEDs and bioimaging. While molecular fluorophores that show bright emission in solution are potential sources of these materials, their emission is frequently lost in the solid state preventing their direct translation to optical applications. Unpredictable packing and coupling of dyes leads to uncontrolled spectral shifts and quenched emission. No universal solution has been found since Perkin made the first synthetic dye 150 years ago. We report the serendipitous discovery of a new type of material that we call small-molecule ionic isolation lattices(SMILES) tackling this long-standing problem. SMILES are easily prepared by adding two equivalents of the anion receptor cyanostar to cationic dyes binding the counter anions and inducing alternating packing of dyes and cyanostar-anion complexes. SMILES materials reinstate solution-like spectral properties and bright fluorescence to thin films and crystals. These positive outcomes derive from the cyanostar. Its wide 3.45-eV band gap allows the HOMO and LUMO levels of the dye to nest inside those of the complex as verified by electrochemistry. This feature simultaneously enables spatial and electronic isolation to decouple the fluorophores from each other and from the cyanostar-anion lattice. Representative dyes from major families of fluorophores, viz, xanthenes, oxazines, styryls, cyanines, and trianguleniums, all crystalize in the characteristic structure and regain their attractive fluorescence. SMILES crystals of rhodamine and cyanine display unsurpassed brightness per volume pointing to uses in demanding applications such as bioimaging. SMILES materials enable predictable fluorophore crystallization to fulfil the promise of optical materials by design.

We developed a colloidal synthesis of CsPbBr3 perovskite nanocrystals (NCs) at a relative low temperature (90 °C) for the bright blue emission which differs from the original green emission (∼510 nm) of CsPbBr3 nanocubes as reported previously. Shapes of the obtained CsPbBr3 NCs can be systematically engineered into single and lamellar-structured 0D quantum dots, as well as face-to-face stacking 2D nanoplatelets and flat-lying 2D nanosheets via tuning the amounts of oleic acid (OA) and oleylamine (OM). They exhibit sharp excitonic PL emissions at 453, 472, 449, and 452 nm, respectively. The large blue shift relative to the emission of CsPbBr3 bulk crystal can be ascribed to the strong quantum confinement effects of these various nanoshapes. PL decay lifetimes are measured, ranging from several to tens of nanoseconds, which infers the higher ratio of exciton radiative recombination to the nonradiative trappers in the obtained CsPbBr3 NCs. These shape-controlled CsPbBr3 perovskite NCs with the bright blue e...

The impact of two kinds of additives, such as 1,8-octanedithiol (ODT), 1,8-diiodooctane (DIO), diphenylether (DPE), and 1-chloronaphthalene (CN), on the performance of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di(2-octyldodecyl)2,2';5',2″;5″,2‴-quaterthiophen-5,5‴-diyl)] (PffBT4T-2OD):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) based polymer solar cell are investigated. The polymer solar cells (PSCs) of PffBT4T-2OD:PC71BM by using CN show a more improved PCE of 10.23%. The solubility difference of PffBT4T-2OD in DIO and CN creates the fine transformation in phase separation and favorable nanoscale morphology. Grazing incidence X-ray diffraction (GIXRD) data clearly shows molecular stacking and orientation of the active layer. Interestingly, DIO and CN have different functions on the effect of the molecular orientation. These interesting studies provide important guidance to optimize and control complicated molecular orientations and nanoscale morphology of PffBT4T-2OD based thick films for the application in PSCs.

The heterodinuclear metal complex OsIr has been designed and synthesized. Upon irradiation with visible light, OsIr exhibits dual luminescence (534 and 721 nm) due to the coexistence of the iridium and osmium activating centers. The cellular uptake of OsIr examined by laser scanning confocal microscopy revealed an apparent nucleolar staining. The iridium moiety interacts with proteins and RNA to trigger a significant luminescence enhancement, whereas the osmium moiety displays a near-infrared luminescence; a ratiometric luminescence response between the two moieties was observed upon protein addition.

A new series of soybean-oil-based elastomers poly(epoxidized soybean oil-co-decamethylene diamine) (PESD) was synthesized by ring-opening polymerization from epoxidized soybean oil (ESO) and decamethylene diamine (DDA) in different molar ratios. The effect of the molar ratio on the structure and properties of PESD was identified by various methods. According to the results of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H NMR) and thermogravimetry (TGA), the glycerol center of ESO was broken by ammonolysis as expected in the process of polymerization, which resulted in un-cross-linked elastomers with low glass transition temperatures (Tg) ranging from −30 to −17 °C. PESD-3 (molar ratio of DDA to ESO is 2:1) was found to have the highest molecular weight and was most suitable for further processing. Then, PESD-3 was successfully cross-linked through succinic anhydride by a general rubber processing method to obtain a cross- linked bioelastomer. The mechanism of chain growth, ammonolysis of ester group, and cross-linking of PESD-3 was studied. The tensile strength of cross-linked PESD could be flexibly adjusted from 0.8 to 8.5 MPa by using different amounts of succinic anhydride without reinforcing fillers. The final bioelastomer possesses good damping property, low water absorption, and low degradation rate in phosphate buffer solution. These properties indicate potential engineering applications. Refereed/Peer-reviewed