Group 13 organometallic complexes are versatile building blocks of supramolecular architectures, offering wide structural and functional diversity. While organoaluminum systems have been extensively explored as nodes or chiral metalloligands in the construction of coordination frameworks, their heavier congeners remain far less investigated. Herein, we examined the reactivity of a new macrocyclic organogallium derivative of 2,3-naphthalenedicarboxylic acid (naphtha-H2), [(Me2Ga)2(naphtha)]2 (1), toward selected mono- and bifunctional pyridine Lewis bases, as well as the chiral metalloligand [Me2Al(CN)]2 (where CN = deprotonated cinchonine). The results show that, in the presence of neutral Lewis bases, the macrocyclic structure of the parent complex 1 undergoes cleavage accompanied by rearrangement into various four-coordinate pyridine adducts, which, in the case of 4,4'-bipyridine (bipy), leads to the formation of a new 1D coordination polymer [(Me2Ga)2(naphtha)(bipy)]n. Moreover, we show that the reaction of 1 with the chiral organoaluminum N,N'-ditopic metalloligand [Me2Al(CN)]2 proceeds via an intriguing transalkylation pathway, affording an original complex [(MeAl)2(naphtha)(CN)2(GaMe3)2]. Together with our previous studies on the organoaluminum analogue of 1, this work provides new insight into how the nature of the Group 13 metal center governs Lewis acidity of organometallic complexes and their reactivity toward N,N'-ditopic linkers.

Abstract Hybrid lead halide perovskitoids with extended 3D connection modes have attracted a lot of attention for optoelectronic and photodetection applications, but up to now, only one example comprising divalent and monovalent cations is known, i.e., MPDA2FAPb4Br13 (MPDA = N-methylpropanediammonium, FA = formamidinium). We expand the family of mixed-cation 3D perovskitoids by introducing three analogues comprising methylammonium (MA), ethylammonium (EA), and dimethylammonium (DMA) cations in small perovskite voids. X-ray diffraction and optical studies show that these compounds adopt a monoclinic system with P2/m symmetry and are examples of 3D perovskitoids exhibiting both narrowband and broadband photoluminescence (PL) and pronounced thermochromism. Analysis of the structural and optical data revealed that the intensity of the broadband PL increases with increasing intraoctahedral distortion, mainly of the corner-sharing PbBr6octahedra. Moreover, using MPDA2MAPb4Br13, we fabricated a single-crystal-based photodetector that performs at a much lower bias voltage (0.5 V) compared to photodetectors based on other 3D perovskitoids (10 V). In addition, the device’s photocurrent remains unchanged after multiple cycles of operation under 448 nm illumination, indicating excellent stability and reliability of the photodetector. All these results not only show that a relaxed tolerance factor applies to 3D perovskitoids, paving the way for expanded structural versatility and optoelectronic tunability in this family of compounds, but also inspire further exploration of these compounds as light-emitting and photodetection materials.

Perovskite solar cells (PSCs) have achieved remarkable power conversion efficiencies (PCEs) and cost-effective fabrication processes. However, defects in the bulk and interfaces of perovskite materials, as well as Li+ migration (especially in n-i-p regular architecture), which are used to enhance the conductivity and hole mobility of spiro-OMeTAD, can significantly impact device performance and stability. Herein, we report a rationally designed meso-crowned porphyrin derivative ([12]-C-4POR) featuring dual macrocyclic binding sites, i.e., a porphyrin core for undercoordinated Pb2+ and a crown ether unit selective for Li+ to suppress surface defects and mitigate lithium-ion migration simultaneously. The incorporation of [12]-C-4POR into perovskite films significantly reduced the trap-state density and suppressed non-radiative recombination, leading to improved charge-carrier dynamics. Devices treated with [12]-C-4POR delivered a champion PCE of 23.14%, surpassing the control device (21.6%), along with enhanced open-circuit voltage (VOC) and fill factor (FF). More importantly, the passivated devices retained ∼95% of their initial PCE after 800 h of continuous operation, compared to ∼55% for the control. This study demonstrates a dual-site host-guest passivation strategy as an effective route to improve both efficiency and operational stability of PSCs.

ABSTRACT The rapid evolution of modern electronic devices has significantly increased the demand of energy storage systems that are lightweight, durable, and capable of delivering both high energy and power densities. Among emerging electrode materials, biomass‐derived activated carbon (BDAC) has gained significant attention as a sustainable and scalable alternative to conventional carbon materials for supercapacitors (SCs). This interest stems from its abundant availability, low cost, tunable porous structure, excellent electrochemical performance, and eco‐friendly production approach. This review systematically summarizes recent advances in BDAC synthesis, structural engineering, composite fabrication, electrolyte selection, and device architecture for SC applications. Particular emphasis is placed on composite engineering strategies integrating metal oxides, conducting polymers (CPs), and MXenes to enhance pseudocapacitive contributions and improve overall energy density. The influence of electrolyte systems including aqueous, organic, and solid‐state configurations on voltage window expansion, ionic transport, and device stability is critically examined. Recent progress in flexible and wearable SC architectures is also highlighted. Finally, key challenges related to scalability, reproducibility, green processing, and long‐term stability are discussed, along with future directions toward industrial‐scale manufacturing of sustainable carbon electrodes. Overall, BDAC‐based SCs represent a promising pathway toward next‐generation eco‐friendly energy storage technologies for portable and wearable electronic devices.

The colloidal synthesis of Ag-based lead-free double perovskite nanocrystals (NCs) involves Ag+-reduction mediated pathways, however, the role of Ag redox chemistry in lattice formation remains poorly understood. Here, we elucidate the crystallization-driven redox processes that govern the formation of Cs2AgBiBr6 NCs. An alternative synthesis has been proposed by carefully studying the effect of reaction temperature behind the in-situ Ag-reduction aided from Ag-oleate complex decomposition at >175 °C, followed by its oxidation mediated by the addition of exclusively used halide precursor, oleylammonium bromide (OLAmBr). The halide precursor participates in the oxidation of in-situ formed Ag0 followed by the crystallization of Cs2AgBiBr6 NCs. This work establishes halide-mediated oxidative etching as a key step in the crystallization of lead-free double perovskite NCs.

Persistent interfacial defects and instability remain key limitations for high-performance perovskite solar cells (PSCs), motivating the development of multifunctional materials that can simultaneously enable efficient charge transport and defect passivation. Here, we report a molecularly engineered dibenzo[g,p]chrysene (DBC)-based core molecule winged by N-(4-methoxyphenyl)pyren-1-amine units, SP-07, designed to operate in two distinct yet complementary roles: as a dopant-free hole-transport material (HTM) and as an interfacial passivation layer. Owing to its planar conjugated core and electron-rich functional groups, SP-07 exhibits high intrinsic hole mobility (∼28.7 × 10-4 cm2/V·s), uniform film formation, and efficient charge extraction. When employed as a standalone HTM, SP-07-based PSCs achieve a stabilized power conversion efficiency (PCE) of 21.7% and demonstrate exceptional operational stability under continuous illumination at 85°C, outperforming spiro-OMeTAD-based reference devices. On the other hand, acting as a passivation layer, SP-07 constructively mitigates under-coordinated Pb2+/halide defects, reduces trap-assisted recombination, improves surface hydrophobicity, and maintains perovskite crystallinity, resulting in devices with a champion PCE exceeding 23%. Outstandingly, passivated devices retain ∼95% of their initial PCE after 1000 h of continuous operation under thermal and illumination stress and maintain structural integrity under ambient conditions for 30 days. These findings demonstrate that the dual functionality of SP-07 enables synergistic improvements in both efficiency and long-term stability, providing a promising strategy for advancing PSCs.

We present a novel approach to enhance the efficiency and stability of inorganic CsPbI2Br based perovskite solar cells (PSCs) through the incorporation of a solvated palladium (Pd) complex, PdBr2(PhCN)2, into perovskite precursor inks (PhCN = benzonitrile). This modification not only stabilizes the α-phase of CsPbI2Br perovskite owing to Pd2+ ions, which were found to be incorporated into the perovskite structure at the B-site, but also effectively improves the perovskite film morphology through the removal of benzonitrile molecules during annealing. Further systematic study reveals that the addition of PdBr2(PhCN)2 results in a better matched energy-level alignment and reduced charge carrier recombination compared to the unmodified material. As a result, the optimized device enables an efficiency of 16.4% with an open-circuit voltage (VOC) of 1.27 V, which outperforms the control device (14.1%, 1.19 V). The device with PdBr2(PhCN)2 shows substantially enhanced environmental and operational stabilities, retaining ≈75% and 90% of their initial PCEs after 500 h aging, respectively. This study demonstrates the potential of B-site engineering via solvated precursors as an effective route toward stable and efficient inorganic perovskite photovoltaics.

We introduce a dual distribution of relaxation (DRT) based approach for analyzing electrochemical impedance spectroscopy (EIS) data in perovskite solar cells (PSCs), combining regression and classification with Bayesian model selection and Havriliak-Negami (HN) modeling to resolve spectra into discrete, Lorentzian-like peaks. This time-domain decomposition offers a powerful alternative for identifying underlying physical processes, such as charge transfer, trap-assisted recombination, and ionic migration by directly extracting characteristic relaxation times (tau). In contrast to traditional equivalent circuit fitting or conventional DRT methods, which often yield broad and overlapping Gaussian-like peaks, our method enables sharper resolution of individual electrochemical signatures. Furthermore, we validated the framework using simulated EIS spectra for two distinct system types, determining the optimal number of peaks (Q) through statistical model selection. Applied to experimental PSC data under varying bias conditions, the approach helps to identify the voltage-dependent relaxation processes, including fast charge transfer (tau similar to 10(-6) s), intermediate trap-mediated recombination (tau similar to 10(-2) s), and slow ionic motion (tau similar to 1 s). Lower-Q models fail to capture low-frequency features such as polarization and charge accumulation, while optimal Q yields accurate, physically meaningful representations of device behavior. This data-driven methodology highlights time-domain DRT as a rigorous and insightful tool for dissecting the complex kinetics that govern PSC performance. (c) 2025 Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

A lead-sulphate passivated MAPbBr3 single crystal based photodetector showcases long-term stable detectivity and a high on–off ratio.

Surface passivation of the perovskite layer is crucial for enhancing the photovoltaic performance of perovskite solar cells (PSCs). Vacuum evaporation is a scalable solvent-free method for depositing a uniform and homogenous thin layer with better control of film thickness. While the use of the vacuum-deposition method to obtain high-quality perovskite thin films is recently adapted, the evaporation of organic additives for surface passivation of the perovskite layer has not been widely studied. In this work, a vacuum evaporation method is introduced to uniformly deposit a novel multifunctional organic salt, 2-chlorophenethylamine pentafluorobenzene sulfonate (2-ClPEAPf), onto a perovskite surface. It is observed that 2-ClPEAPf not only effectively passivates the interfacial defects but also prevents moisture invasion into the perovskite film. As a result, planar n-i-p PSCs exhibit maximum PCE up to 25.16% with an aperture area of 0.1 cm2 and PCE of 24.00% (certified) on an active area of 1.0 cm2. In addition, the 0.1 cm2 device with vacuum-evaporated 2-ClPEAPf reveals enhanced operational stability maintaining 92.5% of its initial efficiency after 800 hours of continuous light irradiation.

Lead halide perovskite quantum dots (QDs) have emerged as next-generation materials for photodetectors (PDs). It is well known that conventional alkyl long-chain ligands show weak binding on the surface of the QD core, leading to low stability and poor charge transfer. Herein, we explore the effect of partial replacing of alkyl long-chain ligands with aromatic short-chain ligands, namely phenylethylamine (PEA) and trans-cinnamic acid (TCA), on the performance of CsPbBr3 QDs-based PD deposited on textile. The planar-type PDs with optimum PEA (L-type) and TCA (X-type) ligand doping concentration show improved performance compared to the control device due to the combined effect of enhanced conductivity and photoluminescence lifetime, lower surface defect centres, and reduced non-radiative recombination. Notably, PEA-treated CsPbBr3 QDs-based PD shows the best photodetection properties of blue light (448 nm) at 10 V with a peak responsivity of 149 mA W-1 and EQE of 41.3%, which is almost 20 times higher than those of the control device and 3 times higher than the TCA-treated CsPbBr3 QDs based device. In addition, this device reveals excellent mechanical and operational stability. These results pave the way for designing flexible and wearable perovskite QDs-based optoelectronic devices, which may find potential applications in future optoelectronic devices.

High defect concentrations at the interfaces are the basis of charge extraction losses and instability in perovskite solar cells. Surface engineering with organic cations is a common practice to solve this issue. However, the full implications of the counteranions of these cations for device functioning are often neglected. In this work, we used 4-fluorophenethylammonium cation with varying halide counteranions for the modification of both interfaces in methylammonium-free Pb-based n-i-p devices, observing significant differences among iodide, bromide, and chloride. The cation treatment of the buried and top interfaces resulted in improved surface quality of the perovskite films and largely improved carrier dynamics with reduced nonradiative recombination. Consequently, the optimal interface-modified methylammonium-free perovskite solar cells surpassed 20% efficiency and demonstrated remarkable operational stability. Our findings underscore the potential of comprehensive surface engineering strategies in advancing the perovskite film and device quality, thereby facilitating their broader and more successful applications.

Metal halide perovskite single crystals (MHPSCs) are highly promising materials for optoelectronic applications, but their stability is hindered by ion migration, thereby impacting their performance. A key factor to understand this issue is calculating the activation energy. Electrochemical Impedance Spectroscopy (EIS) is a powerful technique for separating ionic and electronic processes, yet traditional analysis is labour-intensive, involving extensive measurements, circuit fitting, and manual data interpretation. In this study, we introduce a machine learning (ML)-driven approach to fully automate EIS analysis. EIS data, collected for MAPbI3 and MAPbBr3 across temperatures from 263 K to 343 K, enabled the creation of a large database. The developed ML model predicts EIS spectra at unknown temperatures, fits the appropriate electrical circuit, and automatically extracts passive component values to calculate the activation energy via an Arrhenius plot. This automated workflow streamlines the calculation process, offering fast and reliable activation energy predictions even when temperature data are incomplete or missing. Our approach enhances the efficiency of EIS analysis, providing valuable insights into the stability and performance of MHP SCs.

The modification of the perovskite surface using functional additives is one of the most promising strategies to reduce nonradiative recombination and improve the stability of perovskite solar cells (PSCs). In this work, a novel quaternary pyridinium-based halide salt, 1-ethyl-4-(methoxycarbonyl) pyridinium iodide (EMCP-I), is introduced as an effective post-treatment molecule to improve the quality of the perovskite film. EMCP-I exhibits dual functionality to passivate both negatively and positively charged defects and improve the film morphology. Furthermore, the treatment fine-tunes energy level alignment between the perovskite layer and the hole transport layer (HTL), facilitating more efficient charge transport. Consequently, EMCP-I-treated devices achieve a remarkable power conversion efficiency (PCE) improvement from 20.5% to 22.6%, driven primarily by an enhanced open-circuit voltage (VOC). Beyond efficiency gains, the treatment significantly enhances the environmental and operational stabilities of solar cells. This work provides a guide for tailoring quaternary pyridinium-based molecules for simultaneous improvement of the efficiency and stability of PSCs.

Recent advancements in machine learning (ML) algorithms have transformed Li-Ion battery analysis, focusing on crucial parameters like State of Charge (SOC), State of Health (SOH), and Remaining Useful Life (RUL). However, due to increasing computational complexity and lack of fundamental process understanding within the developed models, conventional predictive tools suffer its integration in real world applications. To address this gap, our study introduces a hybrid modeling approach consisting of two stages. In the first stage, we apply various machine learning algorithms to predict battery degradation using empirical data, focusing on capturing the initial patterns of battery behavior under different operating conditions. In the second stage, we enhance these predictions by integrating Partial Differential Equations (PDEs) that incorporate fundamental physical principles governing battery performance. This combination creates a physics-informed ML model that bridges the gap between empirical data and theoretical understanding. The integration of PDEs significantly improves the model's accuracy in predicting both degradation and discharge capacity. Our results demonstrate a marked enhancement in key performance metrics, with the hybrid model achieving a Mean Square Error (MSE) of 0.2091, Root Mean Square Error (RMSE) of 0.4572 and Mean Absolute Error (MAE) of 0.2555. In comparison, the errors from the initial stage-one ML predictions were substantially higher, with MSE, RMSE, and MAE values of 10.3648, 3.2194, and 0.7392, respectively. These findings highlight the hybrid model's effectiveness and its potential to significantly improve battery management practices, ultimately contributing to the extension of battery lifespan.

Dopant-free HTMs SP-09 and SP-10 are synthesized via a simple method. SP-10 enables 22.1% efficiency and superior stability in PSCs, outperforming spiro-OMeTAD, offering a cost-effective route toward efficient and durable perovskite devices.