A new cyano-substituted olefin-linked COF was synthesized and utilized as a support for palladium nanoparticles. The resulting Pd@CN-COF was demonstrated as a versatile heterogeneous catalyst in cross-coupling reactions, cyanation, and allylic substitution with the productivity exceeding the commercial homogeneous precatalyst [Pd(PPh3)4]. The catalytic activity of Pd@CN-COF was further evaluated in synthetically valuable transformations towards industrially, agrochemically, and pharmacologically relevant products.

ABSTRACT Low‐temperature atomic layer deposition (ALD) is increasingly important for the integration of layered metal dichalcogenides such as tin diselenide (SnSe 2 ) into advanced nanoelectronic devices, where compatibility with temperature‐sensitive substrates and precise thickness control are essential. Using a novel and highly reactive selenium precursor, namely, bis(trimethylstannyl)selenide or Se(SnMe 3 ) 2 , SnSe 2 films are deposited at reduced temperatures. As‐deposited films are initially amorphous, however, post‐deposition annealing at 250°C induces crystallization. Structural analysis reveals a clear evolution in crystallinity: ultrathin films (∼25 nm) exhibit nearly single‐crystalline, defect‐free domains, while thicker films (∼100 nm) transition to a polycrystalline structure. This controlled variation in crystal quality directly influences the electronic transport properties, demonstrating the potential of low‐temperature ALD combined with mild annealing for scalable fabrication of high‐performance, thickness‐engineered SnSe 2 ‐based devices.

The design, synthesis, and comprehensive characterization of six novel halogenated azobenzene acrylate monomers bearing fluorine, chlorine or bromine substituents is reported. The monomers were prepared via a facile three-step synthetic route involving azo-coupling, O-alkylation and O-acylation. Apart from the steady electrochemical properties, halogen substitution proved to be a very useful tool to tune the thermal and optical properties, light-induced switching in particular. Monohalogen derivatives exhibited up to 93% E → Z photoconversion efficiency in solution, whereas the efficiency of dihalogen analogues is lower by 20%, which is ascribed to their nonplanar arrangement. Kinetics studies identified the most stable Z-isomer of the difluoro derivative (τ1/2 = 3.74/6.59 h at 60 °C in DCE/CDCl3). The monofluoro derivative embedded in a polystyrene film demonstrated photoresponsive behavior and remarkable stability by maintaining a macroscopically visible color change for over 90 days. These findings demonstrate that ortho-halogenation is a powerful tool for tuning the properties of photoresponsive materials for potential applications in colorimetric thermal sensing and light-controlled functional systems.

Abstract Multilayer thin film structuring offers a versatile strategy to tailor nanostructures through interface engineering. Atomic layer deposition (ALD) provides precise control of composition and structure via supercycle approaches that enable the multiple metal species introduction. However, the resulting growth behavior is often interpreted without fully accounting for interfacial effects that govern nucleation and nanostructure evolution. In this work, we demonstrate that introducing SnSe2 layers into Sb2Te3/SnSe2 multilayer films using ALD supercycle significantly enhances Sb2Te3 nucleation and accelerates out-of-plane growth, leading to an increase in growth per cycle (GPC) from 0.18 to 0.69 Å/cycle. First-principles atomistic simulations of precursor deposition chemistry and extremely surface-sensitive low-energy ion scattering (LEIS) analysis confirm the promoted growth of Sb2Te3 in Sb2Te3/SnSe2 multilayer structures, which is also accompanied by elemental exchange reactions between Te and Se atoms. The resulting Sb2Te3/SnSe2 multilayer thin films exhibit increased charge carrier and phonon scattering, leading to a significant reduction in lattice thermal conductivity from 1.09 to 0.25 W/mK at room temperature due to the modulated nanostructure. This study establishes a robust analytical framework for understanding and engineering interfacial reactions and nucleation phenomena in ALD-based multilayer systems.

This study reports the design, synthesis, and photophysical investigation of a series of pyrimidinedipyrrolide platinum(II) complexes, including a pyrazine analog. The complexes exhibit square-planar geometries and strong phosphorescence arising from metal-to-ligand charge transfer transitions, as confirmed by X-ray crystallography and time dependent density functional theory (TD-DFT) calculations, respectively. Systematic modification of the C6 substituent on the diazine core and the ancillary ligand enables fine-tuning of the absorption and emission properties. All complexes are emissive in solution (Phi Em comprised between 0.02 and 0.24), with emission maxima spanning 485-592 nm and lifetimes characteristic of phosphorescence (tau 0 ranging from 3.0 to 23.1 & micro;s). Replacement of the pyrimidine core with a pyrazine unit induces a red-shifted but weaker emission.

Herein, a new synthetic procedure for red phosphorus (RP) by atomic layer deposition (ALD) is presented. The deposition of RP thin films was obtained by combining tin tetrachloride and home-synthesized tris(trimethyltin)phosphide. The ALD window was identified between 175 and 200 °C, and the self-limiting nature of the ALD process was verified. The RP thin films deposited on Si/SiO2 wafer, soda lime glass, and carbon paper were extensively characterized by different techniques, revealing that the phosphorus was deposited exclusively as elemental RP without any concomitant phosphorus species. The assessment of the optical properties revealed an optical bandgap of ≈1.9 eV confirming the semiconducting nature of the RP thin films. To gain valuable insight into the ALD reaction mechanism, density functional theory calculations suggested a plausible mechanism that combined ligand exchange and redox steps. This work extends the portfolio of ALD precursors and fills the gap in the missing deposition of elemental P.

Light-conversion agents based on traditional europium complexes absorb/convert only ultraviolet light and leaves the energy of the visible yellow-green light unutilized. The simultaneous and superimposed utilization of ultraviolet and yellow-green light energy can significantly enhance the performance of materials. Hence, we address herein a combined light-conversion agent that can deplete both non-productive and intense ultraviolet and visible light energy. For this purpose, polymerizable phenanthroline and rhodamine B pendants were prepared and copolymerized to afford light-conversion agent (P-Eu) with a dual absorption in both regions. Rhodamine B is used as a receiving antenna transferring energy to the Eu3+ complex-based emissive center. As a result, the P-Eu has significantly enhanced its optical performance (quantum yield increased by 150 %, lifetime increased by 10-27 mu s, and FWHM increased by 18-times). The prepared agent was further dispersed in polylactic acid affording a polymeric film suppressing eventual aggregation and significantly improving thermal/mechanical, and optical properties. The emission maximum is localized at around 620 nm (FWHM similar to 88 nm) with the chromaticity close to the standard red CIE coordinates. Its performance has been significantly enhanced, such as having a stable/enhanced quantum yield (24 %), prolonged fluorescence lifetime (798 and 27 mu s), and providing more red - light components. The film is thermally and mechanically robust, durable, and possesses a minor photobleaching. Its agricultural application has been examined for a lettuce cultivation, which showed significantly improved net photosynthetic rate (64 %), growth rate (1.32-times higher than the control group), biomass accumulation (e.g. fresh weight of aboveground parts increased by 72 %), and nutritional quality (e.g. soluble sugar increased by 44 %).

Taking lithium 2-trifluoromethyl-4,5-dicyanoimidazol-1-ide as a parent lithium salt for Li-ion batteries, systematic property tuning in two series based on variously 2- and 4-substituted 4,5-dicyanoimidazolide and 2-phenyl-4,5-dicyanoimidazolide scaffolds is demonstrated. A straightforward synthetic approach afforded fourteen desired derivatives with a systematically evaluated structure, whose properties were further investigated from various perspectives. The stabilization of the imidazolide anions via the substituent effects was examined using dissociation constants, the Hammett equation, 13C NMR shifts and electronic absorption spectra. Solubility in dimethyl carbonate and 1,2-dimethoxyethane further identified lithium salts with a potential for a practical application, and their solutions were further investigated for aggregation phenomena. Using absorption spectroscopy, a significantly more sensitive and straightforward methodology is presented, which allows the identification of perspective substituents hindering aggregation. The viscosity and density measurements further confirmed the significant property tuning of electrolytes upon changing the structure of lithium dicyanoimidazolide, which is in line with the subsequent electrochemical measurements. Based on the complete gathered data, extension via the 1,4-phenylene moiety along with peripheral (O)CF3-substitution proved to be a useful strategy towards stabilized anions with a promising application in lithium-ion batteries.

Abstract Carbon dots (CDs) are an emerging carbon-based nanomaterial with steadily increasing prospects across agricultural applications, which is mostly due to their easy synthesis, functionalization, small particle size, high biocompatibility, low toxicity, and peculiar optical properties. However, existing studies have largely focused on individual functions or localized mechanisms, with insufficient attention paid to the systemic relationships among material design, functional expression, and plant response. Therefore, this paper adopts a cross-scale perspective to provide a systematic review of the synthesis strategies, functionalization designs, and interaction mechanisms of CDs with plants in agricultural applications. This article also summarizes biomass-based green synthetic methods, highlighting the advantages of simple and scalable approaches, such as hydrothermal and microwave methods in agricultural applications, and further outlines the principles of functionalization design based on the regulation of surface functional groups. The study focuses on the synergistic role of CDs in multifunctional applications, such as promoting nutrient utilization, enhancing stress resistance, and enabling the detection of endogenous plant signals, and proposes their potential role as a multifunctional agricultural nanoplatform. The fundamental interaction mechanisms between CDs and plants, including their absorption, distribution, and transport via the symplastic and apoplastic pathways, are addressed, and emphasize the fundamental links connecting these different processes to real-world agricultural applications. In summary, the recent advances and innovations offer novel strategies for efficient crop yield enhancement, and this review aims to serve as a guide toward targeted design and precise application of high-performance CDs tailored to agricultural needs.

Herein, we present for the first time the synthesis of titanium phosphide (Ti x P y ) by thermal ALD based on in-house synthesized Tris(trimethyltin)phosphide (TMT 3 P) combined with titanium tetrachloride (TiCl 4 ) as the P- and Ti-precursor, respectively.

Twelve model amino-based linear D-pi-A and tripodal D-(pi-A)3 chromophores bearing electron-withdrawing SF5-group(s) at different peripheral positions were designed and prepared in a straightforward way. The influence of the position and the number of SF5-groups was studied with the aid of single crystal X-ray analysis, thermal and electrochemical measurements, (non)linear steady-state and time resolved spectroscopies, and DFT calculations. Significant property tuning can be achieved when modulating the number and position of the (peripheral) SF5-group(s), e.g. increase of the thermal robustness from 300 to 420 degrees C, the HOMO-LUMO gap is tuned through an exclusive manipulation of the LUMO, and the absorption/emission maxima can be red-shifted. The para-positioning allowing their hyperconjugation and the increasing number of the appended SF5-groups along with a polar environment support the intramolecular charge-transfer and open a non-radiative deexcitation channel, while the two-photon absorption cross-section is generally enhanced for the para-substituted octupolar chromophores. Thus, properly placing the SF5-group(s) along the pi-conjugated backbone allows a principal tuning of the push-pull chromophore fundamental function(s).

The last decade unveiled dicyanopyrazine as a purely organic photocatalyst capable of initiating a variety of unprecedented photoredox transformations. The latest discoveries also pointed to a facile Mallory-type photocyclization of the catalyst to quinoxaline-2,3-dicarbonitrile derivative, which proved to be the active catalytic species. Its principal photochemical properties involve the absorption band covering the blue spectral region, a sufficiently long-lived triplet, and the reversible first reduction accompanied by the formation of the corresponding radical anion. Hence, two-photon photoredox catalysis via (consecutive) photoinduced electron transfer can be conveniently accomplished to either oxidize or reduce various substrates. This review summarizes the first synthetic attempts toward dicyanopyrazine catalyst, its further improvements, structural modifications, photochemical properties, and also covers the application of pyrazine-2, 3-dicarbonitirle and quinoxaline-2,3-dicarbonitrile-based photocatalysts across the photoredox catalysis.

Fourteen novel tripodal fluorophores based on a central triphenylamine donor, electron-rich, and polarizable divinylthiophene linker, and eight different fluorine-based substituents have been designed and prepared via a straightforward four-step sequence. Altering the peripheral F-substitution has been demonstrated to largely affect their fundamental properties such as thermal robustness (210-420 °C), the LUMO energies (ELUMO = -2.35 to -3.11 eV), the HOMO-LUMO gap (ΔE = 2.07-2.66 eV), and the absorption/emission maxima (λmax A/E = 442-478/521-678 nm). The experimental data, corroborated by DFT calculations, further revealed twofold and tunable ICT employing both central triphenylamine and auxiliary thiophene donors, and the peripheral F-substitution either boosting or switching-off two-photon absorption activity. Whereas the ─SF5 groups impart an exceptional cross-section of 1930 GM, the ─COCF3 group may completely suppress the nonlinear optical response.

The dynamics and two-photon absorption (2PA) properties of two pyrimidine chromophores are studied using femtosecond time-resolved fluorescence and two-photon excited fluorescence techniques. The pyrimidine is used as an electron withdrawing group and is substituted at the C2 position with a phenylacridan fragment, while diphenylaministyryl donor moieties are appended at positions C4/6 to afford the pseudo-dipolar and pseudo-quadrupolar molecules 1 and 2, respectively. Chromophore 2 shows more efficient fluorescence emission, while 1 exhibits larger Stokes shifts. Their decay pathways are discussed through an emission from a Franck-Condon charge transfer (FC-CT) and a relaxed charge transfer (R-CT) state. Ultrafast dynamics in tetrahydrofuran show population of the R-CT state for 1 that is faster than solvation, while for 2, due to its pseudo-quadrupolar nature, R-CT population is slower and occurs from the solvated FC-CT state. Finally, molecule 2 shows better 2PA properties with cross sections reaching 560 GM at 820 nm.

This study presents the first successful demonstration of growing elemental bismuth (Bi) thin films via thermal atomic layer deposition (ALD) using Bi(NMe2)3 as the precursor and Sb(SiMe3)3 as the co‐reactant. The films were deposited at a relatively low temperature of 100 °C, with a growth per cycle (GPC) of 0.31‐0.34 Å/cycle. Island formation marked the initial growth stages, with surface coverage reaching around 80% after 1000 cycles and full coverage between 2000 and 2500 cycles. Morphological analysis revealed that the Bi grains expanded and became more defined as the number of ALD cycles increased. This coalescence is further supported by X‐ray diffraction (XRD) patterns, which show a preferential shift in growth orientation from the (012) plane to the (003) plane as the film thickness increases. X‐ray photoemission spectroscopy (XPS) confirmed the presence of metallic Bi with minimal surface oxidation. Temperature‐dependent sheet resistance measurements highlight the semimetallic nature of Bi, with a room temperature resistivity of ≈200 µΩcm for the 2500 cycles Bi. Temperature‐dependent sheet resistance was also associated with a transition in carrier‐type dominance from electrons at higher temperatures to holes at lower temperatures.

A novel organic dithienoquinoxaline photoredox catalyst has been immobilized through a straightforward copolymerization approach. The performed heterogenization did not alter fundamental thermal, electrochemical, and optical properties and, most importantly, the ability of the excited catalyst to act either as a one-electron reductant or oxidant using a single light source (similar to 450 nm). The oxidation power of the triplet excited state of both homogeneous and heterogeneous photocatalysts has been demonstrated in the oxidation of sulphides, amines, and alcohols. The photoreduction of nitroaromatics and ketones has been accomplished by utilizing (double-excited) dithienoquinoxaline radical anion. Both oxidation and reduction reactions were accomplished either in batch (homo/heterogeneous) or under continuous-flow conditions using a porous flexible monolithic column with immobilized catalyst. Repetitive cyclic oxidation/reduction of pharmaceutically and industrially important fluorenol/one system along with a consecutive nitro reduction and sulphur oxidation in bis(4-nitrophenyl)sulphide towards an antimalarial agent further demonstrates the wide applicability of the developed catalytic systems/protocols. The recyclability and eventual structural changes of the immobilized catalyst have been addressed through FT-IR spectra and TON/TOF values.

Carbon dots (CDs), as a medium for enhancing photosynthesis, have attracted widespread attention, among which biomass-based CDs are ideal candidate materials owing to their multiple advantages. However, most of the biomass-based CDs are fabricated using a single synthesis strategy and employed directly, lacking rational classification and screening of diverse CD types within the products to identify homologous CDs that could maximize plant photosynthetic utilization efficiency. Hence, two types of CDs, blue (B-CDs) and red (R-CDs), were obtained from tobacco waste through a facile hydrothermal or solvothermal synthesis strategy. The prepared CDs proved to have tunable structures and properties, including tunable photoluminescence. The latter property matched well with the absorption spectra of chlorophyll and enabled the construction of chloroplast/CD hybrid photosynthesis systems. The 1 : 1 combination of B-CDs and R-CDs showed the most pronounced effect on the chloroplast photosynthetic activity, exhibiting a maximum increase of 367%. This significant improvement was attributed to CDs, which converted the energy of ineffective ultraviolet (B-CDs) and yellow-green light (R-CDs), thereby enhancing plant photosynthesis. Further in vivo studies showed that the 1 : 1 mixture of both CDs had a positive effect on light capture and absorption, acceleration of the electron transfer, CO2 assimilatory power, chlorophyll content, photosynthetic activity, psbA gene expression, and Rubisco activity, all of which promoted plant photosynthesis. Improved accumulation of lettuce biomass and nutritional quality were other advantageous effects. In summary, both the developed CDs proved to be very efficient and highly applicable CD-based photosynthetic fertilizers.

The ever-increasing global energy demand together with the environmental issue originated from the use of fossil fuel, has triggered an intense search for sustainable and clean energy alternatives, such us hydrogen energy, biomass and solar energy among others. In this context, a pivotal key to deliver sustainable and superior energy systems lies on the rational design and development of high-quality and cost-effective catalyst offering enhanced stability, activity and selectivity. Consequently, intense efforts have been devoted in the search and synthesis of new catalyst materials to replace the scarce and expensive traditional noble metals (e.g. Pt, Pd, Au and Ru) for energy conversion and energy storage applications. Among the recently explored novel catalyst materials, metal phosphides (MPs) have emerged in recent years, attracting significant attention thanks to their intriguing properties [1]. In particular transition metal phosphides (TMPs) exhibit striking properties. The moderately strong M−P bonds lend outstanding mechanical properties, high thermal stability and outstanding chemical resistance to chemical attack and oxidation in acidic and alkaline solutions. Additionally, Co, Ni, Mo-based phosphides demonstrated excellent catalytic and bifunctional properties, in particular towards water splitting as both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) [2,3]. Herein, we present the synthesis of TMPs by thermal Atomic Layer Deposition (ALD), including titanium phosphide [4], based on the use of different transition metal precursors combined with in-house synthesized P precursors. The physical and chemical properties of the resulting TMPs thin films were extensively characterized by different methods, including atomic force microscopy, X-ray photoelectron spectroscopy and X-Ray diffraction. The presentation will introduce and describe the synthesis of the TMPs and the corresponding characterization toward diverse applications. [1] Z. Pu, T. Liu, I. S. Amiinu, R. Cheng, P. Wang, C. Zhang, P. Ji, W. Hu, J. Liu, S. Mu, Adv. Funct. Mater. , 30 , 2004009 (2020). [2] C.C. Weng, J.T. Ren, Z.Y. Yuan, ChemSusChem , 13 , 3357-3375 (2020). [3] C.-J. Huang, H.-M. Xu, T.-Y. Shuai, Q.-N. Zhan, Z.-J. Zhang, G.-R. Li, Applied Catalysis B: Environmental , 325 , 122313 (2023). [4] R. Zazpe, J. Charvot, J. Rodriguez-Pereira, L. Hromádko,M. Kurka,K. Baishya,H. Sopha, F.Bureš, and J. M. Macak, under revision.