Thermally Stable Anthracene-Based 2D/3D Heterostructures for Perovskite Solar Cells.

Bulky organic cations are used in perovskite solar cells as a protective barrier against moisture, oxygen, and ion diffusion. However, bulky cations can introduce thermal instabilities by reacting with the near-surface of the 3D perovskite forming low-dimensional phases, including 2D perovskites, and by diffusing away from the surface into the film. This study explores the thermal stability of CsFAPbI 3D perovskite surfaces treated with two anthracene salts─anthracen-1-ylmethylammonium iodide (AMAI) and 2-(anthracen-1-yl)ethylammonium iodide (AEAI)─and compares them with the widely used phenethylammonium iodide (PEAI).

Modified Imidazole-Phenol-Based ESIPT Fluorophores as Self-Absorption Free Emitters for Efficient Electroluminescent Devices.

Excited-state intramolecular proton transfer (ESIPT) molecules are promising fluorophores for various applications including bioimaging, sensing, and optoelectronic devices. Particularly, their self-absorption-free fluorescence properties would make them a perfect choice as emissive materials for organic light-emitting diodes (OLEDs). Nevertheless, to become effective emitters some of their properties need to be altered by structural modifications.

Multiple-Temperature-Responsive Double- and Triple-Network Hydrogels.

Temperature-responsive hydrogels which are reversibly activated attract much attention in the field of smart materials. Herein, double- and triple-network hydrogels exhibiting dual- or triple-volume transitions upon changes of temperature are fabricated. Interestingly, the incorporation of superhydrophilic polymer network leads to a significant difference swelling or shrinkage of the multiple-network hydrogels.

Spatiotemporal Retention of Structural Color and Induced Stiffening in Crosslinked Hydroxypropyl Cellulose Beads.

Hydroxypropyl cellulose (HPC) is known for its ability to form cholesteric liquid crystalline phases displaying vivid structural colors. However, these vibrant colors tend to fade over time when the material dries. This issue is a major bottleneck to finding practical applications for these materials.

Mechanically induced polyamorphism in a one-dimensional coordination polymer.

We created different amorphous structures of a coordination polymer by applying mechanical shear forces. One-dimensional Cu(TfN)(bip) (1, TfN = bis(trifluoromethanesulfonyl)imide, bip = 1,3-bis(1-imidazolyl)propane) melted at 245 °C and underwent a glass transition at -10 °C by a static cooling process. 1 formed another amorphous state with a distinct glass transition point of 70 °C under oscillatory shear stress.

CO fixation: cycloaddition of CO to epoxides using practical metal-free recyclable catalysts.

The conversion of CO into valuable chemicals is a crucial field of research. Cyclic organic carbonates have attracted great interest because they can be prepared under mild conditions and because of their structural versatility which enables a large variety of applications. Therefore, there is a need for potent and yet practical catalysts for the cycloaddition of CO to cyclic carbonates that are able to combine availability, low cost and an adequate performance.

Insights into the Synthesis of a Semiconducting Nickel Bis(dithiolene) Coordination Polymer.

Nickel bis(dithiolene) complexes are promising candidates for novel n-type semiconductors, which are air-stable and highly conductive. A key issue for further development is that their synthesis often yields undesired products, greatly limiting the degree of polymerization as well as purity and adversely affecting their electronic properties. Crucially, there is a lack of in-depth identification of these species and understanding of the reaction mechanism.

Mean-Field Theory of the Uniaxial Ferroelectric Smectic A Liquid Crystal Phase.

Following the groundbreaking discovery of the ferroelectric nematic liquid crystal phase (N_{F}), a series of closely-related new polar phases have also been found. An especially interesting one is the ferroelectric smectic A phase (SmA_{F}) with spontaneous polarization along the layer normal observed in a few materials of the N_{F} realm. Here, we present a mean-field molecular model that successfully captures the rich phase diagrams experimentally observed in the literature in terms of two parameters.

Nanothermodynamics: There's Plenty of Room on the Inside.

Nanothermodynamics provides the theoretical foundation for understanding stable distributions of statistically independent subsystems inside larger systems. In this review, it is emphasized that extending ideas from nanothermodynamics to simplistic models improves agreement with the measured properties of many materials. Examples include non-classical critical scaling near ferromagnetic transitions, thermal and dynamic behavior near liquid-glass transitions, and the 1/-like noise in metal films and qubits.

Molecular models of PM6 for non-fullerene acceptor organic solar cells: How DAD and ADA structures impact charge separation and charge recombination.

The quadrupole moment of a non-fullerene acceptor (NFA) generated by the constituent electron donor (D) and acceptor (A) units is a significant factor that affects the charge separation (CS) and charge recombination (CR) processes in organic photovoltaics (OPVs). However, its impact on p-type polymer domains remains unclear. In this study, we synthesized p-type molecules, namely acceptor-donor-acceptor (ADA) and donor-acceptor-donor (DAD), which are components of the benchmark PM6 polymer (D: benzodithiophene and A: dioxobenzodithiophene).

Decarboxylative Cross-Coupling Enabled by Fe and Ni Metallaphotoredox Catalysis.

Decarboxylative cross-coupling of carboxylic acids and aryl halides has become a key transformation in organic synthesis to form C(sp)-C(sp) bonds. In this report, a base metal pairing between Fe and Ni has been developed with complementary reactivity to the well-established Ir and Ni metallaphotoredox reactions. Utilizing an inexpensive FeCl cocatalyst along with a pyridine carboxamidine Ni catalyst, a range of aryl iodides can be preferentially coupled to carboxylic acids over boronic acid esters, triflates, chlorides, and even bromides in high yields.

Conversion of Carbon Dioxide into Molecular-based Porous Frameworks.

ConspectusThe conversion of carbon dioxide (CO) to value-added functional materials is a major challenge in realizing a carbon-neutral society. Although CO is an attractive renewable carbon resource with high natural abundance, its chemical inertness has made the conversion of CO into materials with the desired structures and functionality difficult. Molecular-based porous materials, such as metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs), are designable porous solids constructed from molecular-based building units.

Nanodots functionalized with chitooligosaccharides for blocking chitoporins.

We report the synthesis of functionalized nanodots as potential powerful blockers of solute transport through a chitoporin. Ultrasmall silica nanocapsules with a diameter of ∼ 6 nm were coated with chitooligosaccharides to be used as a "lid" binding to the opening of the chitoporin VhChiP of Vibrio campbellii. Efficient blocking is attributed to the adequate size of the nanodots and their functionalization with oligochitosan, which has strong affinity towards the Vibrio chitoporin.

Systematic design and functionalisation of amorphous zirconium metal-organic frameworks.

Controlling the structure and functionality of crystalline metal-organic frameworks (MOFs) using molecular building units and post-synthetic functionalisation presents challenges when extending this approach to their amorphous counterparts (aMOFs). Here, we present a new bottom-up approach for synthesising a series of Zr-based aMOFs, which involves linking metal-organic clusters with specific ligands to regulate local connectivity. In addition, we overcome the limitations of post-synthetic modifications in amorphous systems, demonstrating that homogeneous functionalisation is achievable even without regular internal voids.

Construction of 2D zinc(II) MOFs with tricarboxylate and N-donor mixed ligands for multiresponsive luminescence sensors and CO adsorption.

The solvothermal reactions of ZnCl·6HO, benzene-1,3,5-tribenzoic acid (Hbtb), and N-heterocyclic ancillary imidazole (Im) or aminopyrimidine (a mp) ligands led to the creation of two-dimensional (2D) zinc(II) based metal-organic frameworks (MOFs), (MeNH)[Zn(btb)(Im)]·2DMF·3MeOH (1) and (MeNH)[Zn(btb)(amp)]·HO·2DMF·MeOH (2). The btb ligands in 1 and 2 form an anionic 2D layered structure with a (6) honeycomb (hcb) topology by linking to Zn(II) centres through their carboxylate groups. The incorporation of N-heterocyclic auxiliary ligands Im and amp into the hcb nets resulted in the formation of a 2D hydrogen-bonded and covalently pillared bilayer structure featuring two-fold interpenetrating networks.

Computational Study of Carbon Dioxide Capture by Tertiary Amines.

The reaction mechanisms and corresponding structure-activity relationships of tertiary amines with respect to CO capture have been investigated using density functional theory (DFT) calculations. The reaction mechanism for CO capture via base-catalyzed hydration to form bicarbonate is proposed to proceed in a single step involving proton transfer and the formation of a carbon-oxygen bond. Based on the height of the reaction barriers, we suggest that amines containing side chains with the ethyl group, along with a single hydroxyl group, and cyclic structures, are especially active for CO capture.

Reactive Passivation of Wide-Bandgap Organic-Inorganic Perovskites with Benzylamine.

While amines are widely used as additives in metal-halide perovskites, our understanding of the way amines in perovskite precursor solutions impact the resultant perovskite film is still limited. In this paper, we explore the multiple effects of benzylamine (BnAm), also referred to as phenylmethylamine, used to passivate both FACsPb(IBr) and FACsPbI perovskite compositions. We show that, unlike benzylammonium (BnA) halide salts, BnAm reacts rapidly with the formamidinium (FA) cation, forming new chemical products in solution and these products passivate the perovskite crystal domains when processed into a thin film.

Efficient dye removal using manganese oxide-modified nanocellulosic films from sugarcane bagasse.

Removing toxic dyes from industrial wastewater is crucial for environmental protection. This research introduced novel composite films of manganese oxide (MnO)-modified nanocellulose (MCel) and unmodified nanocellulose (Cel) derived from sugarcane bagasse for dye removal. Nanocellulose was extracted from sugarcane bagasse and subsequently transformed into MCel through in-situ MnO synthesis.

Tuning Electronic and Proton Transfer Properties on Amino-Functionalized Co-Based MOF for Efficient Photocatalytic Hydrogen Evolution.

Efficient hydrogen (H) production through photocatalytic water splitting was achieved by using an amino-functionalized azolate/cobalt-based metal-organic framework (MOF). While previous reports highlighted the amino group's role only as a substituent group for enabling light absorption of MOFs in the visible region, our present study revealed its dual role. The amino substituent not only acts as an electron donor to increase the electron availability at the active Co sites but also provides hydrogen-hopping sites within the pore channel, facilitating proton (H) diffusion along the framework.

characterization techniques of protein corona around nanomaterials.

Nanoparticles (NPs) inevitably interact with proteins upon exposure to biological fluids, leading to the formation of an adsorption layer known as the "protein corona". This corona imparts NPs with a new biological identity, directly influencing their interactions with living systems and dictating their fates . Thus, gaining a comprehensive understanding of the dynamic interplay between NPs and proteins in biological fluids is crucial for predicting therapeutic effects and advancing the clinical translation of nanomedicines.

Entropically driven melting of Cu-based 1D coordination polymers.

We investigated the melting behavior of four CPs with one-dimensional structures from a thermodynamic point-of-view. The difference in melting points depending on the crystal structures is observed. The interactions within the crystals were analyzed using DFT calculations.

Alloying One-Dimensional Coordination Polymers To Create Ductile Materials.

The preparation of coordination polymer (CP) alloys is demonstrated by the use of two meltable, one-dimensional crystal structures via melt-kneading. The polymer structures of the alloys are studied by synchrotron X-ray absorption and scattering, solid-state NMR spectroscopy, DSC, and viscoelastic measurements. Crystalline and amorphous domains and thermal properties (melting and glass transition) in the alloys depend on the ratio of the two constituent CPs.

Full-scale polymer relaxation induced by single-chain confinement enhances mechanical stability of nanocomposites.

Polymer nanocomposites with tuning functions are exciting candidates for various applications, and most current research has focused on static mechanical reinforcement. Actually, under service conditions of complex dynamic interference, stable dynamic mechanical properties with high energy dissipation become more critical. However, nanocomposites often exhibit a trade-off between static and dynamic mechanics, because of their contradictory underlying physics between chain crosslinking and chain relaxation.