Amrithakrishnan Bindhu, Jawahar I. Naseemabeevi, Subodh Ganesanpotti
Tuning the photophysical response is indispensable in realizing the full potential of phosphors to meet the demands of multifunctional applications, such as solid-state lighting and optical thermometry. Herein, orange-red emission from an Sm3+-based Li3Y3Te2O12 system was studied for the first time with CIE coordinates of (0.488, 0.406), an internal quantum efficiency of 26%, T1/2 of 500 K, CCT of 2346 K and color purity of 68%. The fabricated orange-emitting devices presented bright orange-red emission and superior color stability even at higher input currents suitable for plant growth and lighting applications with CIE coordinates of (0.444, 0.276) at 50 mA. The enhancement in temperature sensitivity of the system was achieved via a co-doping strategy by introducing Tb3+ ions. An improved relative temperature sensitivity of 1.8% K−1 in the physiological temperature range was obtained based on the fluorescence intensity ratio method aided by the efficient energy transfer from Tb3+ to Sm3+. Thus, the present work demonstrates the multifunctional properties of the Li3Y3Te2O12:Tb3+/Sm3+ phosphor in solid-state lighting and ratiometric temperature sensing.
{"title":"Engineering the multifunctionality of Li3Y3Te2O12 garnets with Sm3+ and Tb3+ activators for solid-state lighting and luminescence thermometry","authors":"Amrithakrishnan Bindhu, Jawahar I. Naseemabeevi, Subodh Ganesanpotti","doi":"10.1039/d4dt02483d","DOIUrl":"https://doi.org/10.1039/d4dt02483d","url":null,"abstract":"Tuning the photophysical response is indispensable in realizing the full potential of phosphors to meet the demands of multifunctional applications, such as solid-state lighting and optical thermometry. Herein, orange-red emission from an Sm<small><sup>3+</sup></small>-based Li<small><sub>3</sub></small>Y<small><sub>3</sub></small>Te<small><sub>2</sub></small>O<small><sub>12</sub></small> system was studied for the first time with CIE coordinates of (0.488, 0.406), an internal quantum efficiency of 26%, <em>T</em><small><sub>1/2</sub></small> of 500 K, CCT of 2346 K and color purity of 68%. The fabricated orange-emitting devices presented bright orange-red emission and superior color stability even at higher input currents suitable for plant growth and lighting applications with CIE coordinates of (0.444, 0.276) at 50 mA. The enhancement in temperature sensitivity of the system was achieved <em>via</em> a co-doping strategy by introducing Tb<small><sup>3+</sup></small> ions. An improved relative temperature sensitivity of 1.8% K<small><sup>−1</sup></small> in the physiological temperature range was obtained based on the fluorescence intensity ratio method aided by the efficient energy transfer from Tb<small><sup>3+</sup></small> to Sm<small><sup>3+</sup></small>. Thus, the present work demonstrates the multifunctional properties of the Li<small><sub>3</sub></small>Y<small><sub>3</sub></small>Te<small><sub>2</sub></small>O<small><sub>12</sub></small>:Tb<small><sup>3+</sup></small>/Sm<small><sup>3+</sup></small> phosphor in solid-state lighting and ratiometric temperature sensing.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"73 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hybrid coordination polimers based on AgX (with X = Cl, Br) and 2-, 3-, 4-picolylamine ligands, obtained by means of solvent-free methods, show peculiar luminescence properties that are strongly influenced by their structural motif, which in turn is defined by the isomer of the picolylamine molecule present. A comprehensive study, combining photophysical methods and DFT calculations, allowed to rationalize the emissive behaviour of such hybrid coordination polymers in relation to their crystal structures and electronic properties. By means of luminescence measurements at variable temperatures, the nature of the emissive excited-states and their deactivation dynamics was interpreted, revealing XMLCT transitions in the [(AgX)(2-pica)]n compounds, a TADF behaviour in the case of 3-pica derivatives, while dual emission at room temperature was detected for the [(AgX)(4-pica)]n family. The presence of low energy CC states, permitted by argentophilic interactions, is also considered in [(AgX)(2-pica)]n, whose structures are characterized by single/double inorganic chains, and in [(AgX)(4-pica)]n, where discrete dimeric Ag2X2 units are present. These findings open new avenues for the design and application of luminescent AgX-based hybrid materials.
{"title":"Rationalization of the structural, electronic and photophysical properties of silver(I) halide n-picolylamine hybrid coordination polymers.","authors":"Caterina Zuffa, Daniele Veclani, Marianna Marchini, Filippo Monti, Chiara Cappuccino, Lucia Maini, Barbara Ventura","doi":"10.1039/d4dt03003f","DOIUrl":"https://doi.org/10.1039/d4dt03003f","url":null,"abstract":"Hybrid coordination polimers based on AgX (with X = Cl, Br) and 2-, 3-, 4-picolylamine ligands, obtained by means of solvent-free methods, show peculiar luminescence properties that are strongly influenced by their structural motif, which in turn is defined by the isomer of the picolylamine molecule present. A comprehensive study, combining photophysical methods and DFT calculations, allowed to rationalize the emissive behaviour of such hybrid coordination polymers in relation to their crystal structures and electronic properties. By means of luminescence measurements at variable temperatures, the nature of the emissive excited-states and their deactivation dynamics was interpreted, revealing XMLCT transitions in the [(AgX)(2-pica)]<small><sub>n</sub></small> compounds, a TADF behaviour in the case of 3-pica derivatives, while dual emission at room temperature was detected for the [(AgX)(4-pica)]<small><sub>n</sub></small> family. The presence of low energy CC states, permitted by argentophilic interactions, is also considered in [(AgX)(2-pica)]<small><sub>n</sub></small>, whose structures are characterized by single/double inorganic chains, and in [(AgX)(4-pica)]<small><sub>n</sub></small>, where discrete dimeric Ag<small><sub>2</sub></small>X<small><sub>2</sub></small> units are present. These findings open new avenues for the design and application of luminescent AgX-based hybrid materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xinglu Wang, Qing Ma, Sen Yin, Ting Gao, Pengfei Yan, Yanyan Zhou, Hongfeng Li
Herein, we report the influence of solvent on the self-assembly of a dinuclear helicate, (NMe4)2[Eu2(LR)4]. A multiple species mixture with the chemical composition of [Eu2(LR)2n]n‒ present in CH₃CN, can be transformed into a helicate upon increasing the content of CHCl₃, accompanied by a significant enhancement in circularly polarized luminescence activity.
{"title":"Solvent induced self-assembly of dinuclear Eu(III) helicate and emergent strong CPL","authors":"Xinglu Wang, Qing Ma, Sen Yin, Ting Gao, Pengfei Yan, Yanyan Zhou, Hongfeng Li","doi":"10.1039/d4dt02934h","DOIUrl":"https://doi.org/10.1039/d4dt02934h","url":null,"abstract":"Herein, we report the influence of solvent on the self-assembly of a dinuclear helicate, (NMe4)2[Eu2(LR)4]. A multiple species mixture with the chemical composition of [Eu2(LR)2n]n‒ present in CH₃CN, can be transformed into a helicate upon increasing the content of CHCl₃, accompanied by a significant enhancement in circularly polarized luminescence activity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142911454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Carbon monoxide (CO) is widely acknowledged as a significant environmental pollutant allied to numerous instances of accidental poisoning in humans. However, it also serves a pivotal role as a signaling molecule in plants, exhibiting functions analogous to those of other gaseous signaling molecules, including nitric oxide (NO) and hydrogen sulfide (H2S). In the context of plant physiology, CO is synthesized as an integral component of the defense mechanism against oxidative damage, particularly under abiotic stress conditions such as drought, salinity, and exposure to heavy metals. Current research methodologies have demonstrated a deficiency in effective tools for monitoring CO dynamics in plants during periods of stress under heavy metals accumulation across various developmental stages. Therefore, developing a sensor capable of detecting CO in living plant tissues is essential, facilitating a deeper understanding of its biological functions, underlying mechanisms, and metabolic pathways. In response to this gap, the present study introduces a novel technique for monitoring CO production and its activity in plants using Nitrogen-doped Carbon Quantum Dots (N-CQDs). These nanodots exhibit exceptional biocompatibility, low toxicity, and environmentally sustainable characteristics, rendering them an optimal instrument for CO detection via fluorescence quenching mechanism with a detection limit (LOD) of 0.102 μM. This innovative nanomarker facilitates the detection of trace quantities of CO within plant cells, providing new insights into the stress responses of plants in the presence of heavy metals such as Cu, Zn, Pb, Ru, Cr, Cd, and Hg and the processes involved in seed germination. Additionally, confocal microscopy has validated the interaction between CO and N-CQDs, yielding visual evidence of CO binding within plant cells, further enhancing the understanding of CO's role in plant biology.
{"title":"Monitoring of CO as a plant signaling molecule under heavy metal stress using carbon nanodots","authors":"Shrodha Mondal, Olivia Sarkar, Santi M Mandal, Ansuman Chattopadhyay, Prithidipa Sahoo","doi":"10.1039/d4dt03101f","DOIUrl":"https://doi.org/10.1039/d4dt03101f","url":null,"abstract":"Carbon monoxide (CO) is widely acknowledged as a significant environmental pollutant allied to numerous instances of accidental poisoning in humans. However, it also serves a pivotal role as a signaling molecule in plants, exhibiting functions analogous to those of other gaseous signaling molecules, including nitric oxide (NO) and hydrogen sulfide (H2S). In the context of plant physiology, CO is synthesized as an integral component of the defense mechanism against oxidative damage, particularly under abiotic stress conditions such as drought, salinity, and exposure to heavy metals. Current research methodologies have demonstrated a deficiency in effective tools for monitoring CO dynamics in plants during periods of stress under heavy metals accumulation across various developmental stages. Therefore, developing a sensor capable of detecting CO in living plant tissues is essential, facilitating a deeper understanding of its biological functions, underlying mechanisms, and metabolic pathways. In response to this gap, the present study introduces a novel technique for monitoring CO production and its activity in plants using Nitrogen-doped Carbon Quantum Dots (N-CQDs). These nanodots exhibit exceptional biocompatibility, low toxicity, and environmentally sustainable characteristics, rendering them an optimal instrument for CO detection via fluorescence quenching mechanism with a detection limit (LOD) of 0.102 μM. This innovative nanomarker facilitates the detection of trace quantities of CO within plant cells, providing new insights into the stress responses of plants in the presence of heavy metals such as Cu, Zn, Pb, Ru, Cr, Cd, and Hg and the processes involved in seed germination. Additionally, confocal microscopy has validated the interaction between CO and N-CQDs, yielding visual evidence of CO binding within plant cells, further enhancing the understanding of CO's role in plant biology.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"353 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142911565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Milan Maďar, Jan Faltejsek, Hana Bušková, Lucie Koláčná, Adam Jaroš, Jan Kotek, Michal Straka, Vojtech Kubicek, Jiri Ludvik
Copper isotopes and their complexes are intensively studied due to their high potential for the application in radiodiagnosis and radiotherapy. Here we study the CuII complex of 1,8-bis(2-hydroxybenzyl)-cyclam (H2L) that forms unexpected versatility of isomers differing in the mutual orientation of substituents on cyclam nitrogen atoms, protonation of phenolate pendant, and ligand denticity. The interconversion of isomers is rather slow, which made the isolation, identification and investigation of some of the individual species possible. The most stable and the most common form is the hexacoordinated trans-III isomer. However, several other forms were also observed in solution in the course of HPLC, UV-VIS and electrochemical measurements. The isomers present in solution were identified by comparison with the solid-state structures solved by X-ray diffraction analysis on single crystals and with the help of theoretical calculations. The phenolate pendant is coordinated both in the protonated and deprotonated state, however, the coordination in axial position of the hexacoordinated trans-III complex is weak, especially in its protonated state. On the other hand, CuII ion is pentacoordinated in the isomer cis-V with only one phenolate strongly coordinated in the basal plane of the distorted tetragonal pyramid. The computational data showed that the phenolate groups might form strong intraligand hydrogen bonds competitive to the metal-phenolate bonds, stabilizing the structure of the complex. In addition, theoretical calculations revealed that several geometries are energetically close to the optimal one, which indicates possible dynamic behaviour of the complex in the solution.
{"title":"Unusual variability of isomers in copper(II) complexes with 1,8-bis(2-hydroxybenzyl)-cyclam","authors":"Milan Maďar, Jan Faltejsek, Hana Bušková, Lucie Koláčná, Adam Jaroš, Jan Kotek, Michal Straka, Vojtech Kubicek, Jiri Ludvik","doi":"10.1039/d4dt03166k","DOIUrl":"https://doi.org/10.1039/d4dt03166k","url":null,"abstract":"Copper isotopes and their complexes are intensively studied due to their high potential for the application in radiodiagnosis and radiotherapy. Here we study the Cu<small><sup>II</sup></small> complex of 1,8-bis(2-hydroxybenzyl)-cyclam (H<small><sub>2</sub></small>L) that forms unexpected versatility of isomers differing in the mutual orientation of substituents on cyclam nitrogen atoms, protonation of phenolate pendant, and ligand denticity. The interconversion of isomers is rather slow, which made the isolation, identification and investigation of some of the individual species possible. The most stable and the most common form is the hexacoordinated <em>trans</em>-<strong>III</strong> isomer. However, several other forms were also observed in solution in the course of HPLC, UV-VIS and electrochemical measurements. The isomers present in solution were identified by comparison with the solid-state structures solved by X-ray diffraction analysis on single crystals and with the help of theoretical calculations. The phenolate pendant is coordinated both in the protonated and deprotonated state, however, the coordination in axial position of the hexacoordinated <em>trans</em>-<strong>III</strong> complex is weak, especially in its protonated state. On the other hand, Cu<small><sup>II</sup></small> ion is pentacoordinated in the isomer <em>cis</em>-<strong>V</strong> with only one phenolate strongly coordinated in the basal plane of the distorted tetragonal pyramid. The computational data showed that the phenolate groups might form strong intraligand hydrogen bonds competitive to the metal-phenolate bonds, stabilizing the structure of the complex. In addition, theoretical calculations revealed that several geometries are energetically close to the optimal one, which indicates possible dynamic behaviour of the complex in the solution.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"27 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Airton Bispo, Jr., Diogo A. Galico, Jeffrey S. Ovens, Fernando Aparecido Sigoli, Muralee Murugesu
Lanthanide-based Single-Molecule Magnets (SMMs) with opto-magnetic properties provide a means to understand intrinsic energy levels of 4f ions and their influence on optical and magnetic behaviour. Fundamental understanding of their luminescent and slow relaxation of the magnetzation behaviour is critical for targetting and designing SMMs with multifunctionalities. Herein, we seek to investigate the role of DyIII coordination environment and fine electronic structure on the slow magnetic relaxation and luminescent thermometry. Our findings are illustrated through two distinct DyIII complexes, [Dy2bpm(hexd)6] (1) and [Dy2bpm(hpd)6] (2), (bpm = 2,20-bipyrimidine, hexd = 2,4-hexanedione, hpd = 3,5-Heptanedione), by comparing their features with a family of DyIII dinuclear species bridged by bpm. These findings highlight that the hexd- and hpd- ligand yields similar effective barrier to the reversal of magnetization (280 – 290 K). The values are among the highest for dinuclear DyIII complexes bridged by bpm, due to the low distortion of the DyIII coordination polyhedra and the long Dy–N equatorial bonds. Furthermore, the luminescence performance is affected by the triplet state energy of the terminal ligand, influencing ligand-to-DyIII energy transfer. The hpd- ligand's higher T1 state energy leads to poor ligand-to-DyIII energy transfer, limiting the use of 2 for luminescence thermometry. Conversely, this issue is absent in 1, which offers a relative thermal sensitivity of 0.1 to 0.7% K-1 (10 to 60 K) with a temperature uncertainty below 1 K. These findings contribute to our understanding of lanthanide-based SMMs and facilitate the design of multifunctional materials with tailored magnetic and luminescent properties for molecular electronics and beyond.
{"title":"Impacts of β-Diketonate Terminal Ligands on Slow Magnetic Relaxation and Luminescence Thermometry in Dinuclear DyIII Single-Molecule Magnets Leveraging Subtle Local Coordination Modifications to Refine the Slow Relaxation of Magnetization and Enhance Luminescence Thermometry in Dinuclear DyIII Single-Molecule Magnets","authors":"Airton Bispo, Jr., Diogo A. Galico, Jeffrey S. Ovens, Fernando Aparecido Sigoli, Muralee Murugesu","doi":"10.1039/d4dt02200a","DOIUrl":"https://doi.org/10.1039/d4dt02200a","url":null,"abstract":"Lanthanide-based Single-Molecule Magnets (SMMs) with opto-magnetic properties provide a means to understand intrinsic energy levels of 4f ions and their influence on optical and magnetic behaviour. Fundamental understanding of their luminescent and slow relaxation of the magnetzation behaviour is critical for targetting and designing SMMs with multifunctionalities. Herein, we seek to investigate the role of DyIII coordination environment and fine electronic structure on the slow magnetic relaxation and luminescent thermometry. Our findings are illustrated through two distinct DyIII complexes, [Dy2bpm(hexd)6] (1) and [Dy2bpm(hpd)6] (2), (bpm = 2,20-bipyrimidine, hexd = 2,4-hexanedione, hpd = 3,5-Heptanedione), by comparing their features with a family of DyIII dinuclear species bridged by bpm. These findings highlight that the hexd- and hpd- ligand yields similar effective barrier to the reversal of magnetization (280 – 290 K). The values are among the highest for dinuclear DyIII complexes bridged by bpm, due to the low distortion of the DyIII coordination polyhedra and the long Dy–N equatorial bonds. Furthermore, the luminescence performance is affected by the triplet state energy of the terminal ligand, influencing ligand-to-DyIII energy transfer. The hpd- ligand's higher T1 state energy leads to poor ligand-to-DyIII energy transfer, limiting the use of 2 for luminescence thermometry. Conversely, this issue is absent in 1, which offers a relative thermal sensitivity of 0.1 to 0.7% K-1 (10 to 60 K) with a temperature uncertainty below 1 K. These findings contribute to our understanding of lanthanide-based SMMs and facilitate the design of multifunctional materials with tailored magnetic and luminescent properties for molecular electronics and beyond.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"14 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142911567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Namonarayan Meena, Supriya Sahoo, Nilotpal Deka, Vinayak B. Gadagin, Jan Kazimierz Zaręba, Ramamoorthy Boomishankar
Organic-inorganic hybrid ferroelectric compounds of the halobismuthates family have emerged as a focal point of research owing to their reduced toxicity and distinctive optical characteristics. This study presents a novel ammonium hybrid perovskite, [BPMBDMA]∙[Bi2Br9], which exhibits both ferro- and piezoelectric properties and crystallizes in the polar noncentrosymmetric Pca21 space group. The nonlinear optical (NLO) activity of [BPMBDMA]∙[Bi2Br9] was corroborated through second harmonic generation measurements evidencing its noncentrosymmetric structure, which was further substantiated by piezoresponse force microscopy analyses. Ferroelectric P-E hysteresis loop investigations conducted on a thin film sample of [BPMBDMA]∙[Bi2Br9] revealed a saturation polarization (Ps) as much as 11.30 µC cm−2 at ambient temperature. To explore the piezoelectric energy harvesting capabilities of [BPMBDMA]∙[Bi2Br9], composite materials were fabricated using polylactic acid (PLA) as a matrix. Notably, a device comprising 10 wt% [BPMBDMA]∙[Bi2Br9] in PLA demonstrated a remarkable output voltage of 24.6 V and a peak power density of 13.65 µW cm−2. The practical applicability of this device’s output performance was further evaluated through a capacitor charging experiment, wherein a 10 µF capacitor was charged within 160 seconds.
{"title":"Ferroelectricity and Piezoelectric Energy Harvesting of an A3M2X9-type 0D Bromobismuthate Hybrid with Bulky Organic Quaternary Amine","authors":"Namonarayan Meena, Supriya Sahoo, Nilotpal Deka, Vinayak B. Gadagin, Jan Kazimierz Zaręba, Ramamoorthy Boomishankar","doi":"10.1039/d4dt03225j","DOIUrl":"https://doi.org/10.1039/d4dt03225j","url":null,"abstract":"Organic-inorganic hybrid ferroelectric compounds of the halobismuthates family have emerged as a focal point of research owing to their reduced toxicity and distinctive optical characteristics. This study presents a novel ammonium hybrid perovskite, <strong>[BPMBDMA]∙[Bi<small><sub>2</sub></small>Br<small><sub>9</sub></small>]</strong>, which exhibits both ferro- and piezoelectric properties and crystallizes in the polar noncentrosymmetric <em>Pca</em>2<small><sub>1</sub></small> space group. The nonlinear optical (NLO) activity of <strong>[BPMBDMA]∙[Bi<small><sub>2</sub></small>Br<small><sub>9</sub></small>]</strong> was corroborated through second harmonic generation measurements evidencing its noncentrosymmetric structure, which was further substantiated by piezoresponse force microscopy analyses. Ferroelectric <em>P</em>-<em>E</em> hysteresis loop investigations conducted on a thin film sample of <strong>[BPMBDMA]∙[Bi<small><sub>2</sub></small>Br<small><sub>9</sub></small></strong>] revealed a saturation polarization (<em>P</em><small><sub>s</sub></small>) as much as 11.30 µC cm<small><sup>−2</sup></small> at ambient temperature. To explore the piezoelectric energy harvesting capabilities of <strong>[BPMBDMA]∙[Bi<small><sub>2</sub></small>Br<small><sub>9</sub></small>]</strong>, composite materials were fabricated using polylactic acid (PLA) as a matrix. Notably, a device comprising 10 wt% <strong>[BPMBDMA]∙[Bi<small><sub>2</sub></small>Br<small><sub>9</sub></small>]</strong> in PLA demonstrated a remarkable output voltage of 24.6 V and a peak power density of 13.65 µW cm<small><sup>−2</sup></small>. The practical applicability of this device’s output performance was further evaluated through a capacitor charging experiment, wherein a 10 µF capacitor was charged within 160 seconds.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"71 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142911564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Silicon is utilized as a functional material in various fields such as semiconductors, bio-medicine, and solar energy. To prepare Si materials, researchers have proposed methods including carbothermal reduction, hydrothermal reduction, and magnesiothermal reduction, but these strategies often involve high temperatures or unwanted by-products. Herein, we present a room-temperature ionic liquid reduction system to prepare Si nanospheres based on 1-butyl-3-methylimidazolium chloride-aluminum chloride ([Bmim]Cl-AlCl3). In this room-temperature solution system, AlCl3 not only absorbs the heat generated in the reaction, but also can be reduced by metallic Mg to active intermediates, which participates in the reduction of the SiO2. Furthermore, spherical SiO2 can be gently reduced to spherical nano-Si with preserved morphology in the [Bmim]Cl-AlCl3 system. When the prepared Si nanosphere electrode is employed as the anode in lithium-ion batteries, it demonstrates an initial Coulombic efficiency of 82.9% and capacity retention of 94.2% after 100 cycles at 0.5 A g-1. Moreover, the SVC electrode, obtained by reducing SiO2@C, exhibits almost no capacity decay after 100 cycles and retains a specific capacity of 914 mA h g-1 after 600 cycles at 2 A g-1. This study provides an alternative, mild preparative route to Si-based functional materials with preserved morphology and components of the Si-precursors.
{"title":"A Low-temperature Ionic Liquid System to Topochemically Synthesize Si Nanospheres for High-performance Lithium-ion Batteries","authors":"Yanan Xu, shiyue Zhang, Yu Zhang, Qing Hu, Hao Li, wenkai Wang, Hongbin Du","doi":"10.1039/d4dt03315a","DOIUrl":"https://doi.org/10.1039/d4dt03315a","url":null,"abstract":"Silicon is utilized as a functional material in various fields such as semiconductors, bio-medicine, and solar energy. To prepare Si materials, researchers have proposed methods including carbothermal reduction, hydrothermal reduction, and magnesiothermal reduction, but these strategies often involve high temperatures or unwanted by-products. Herein, we present a room-temperature ionic liquid reduction system to prepare Si nanospheres based on 1-butyl-3-methylimidazolium chloride-aluminum chloride ([Bmim]Cl-AlCl3). In this room-temperature solution system, AlCl3 not only absorbs the heat generated in the reaction, but also can be reduced by metallic Mg to active intermediates, which participates in the reduction of the SiO2. Furthermore, spherical SiO2 can be gently reduced to spherical nano-Si with preserved morphology in the [Bmim]Cl-AlCl3 system. When the prepared Si nanosphere electrode is employed as the anode in lithium-ion batteries, it demonstrates an initial Coulombic efficiency of 82.9% and capacity retention of 94.2% after 100 cycles at 0.5 A g-1. Moreover, the SVC electrode, obtained by reducing SiO2@C, exhibits almost no capacity decay after 100 cycles and retains a specific capacity of 914 mA h g-1 after 600 cycles at 2 A g-1. This study provides an alternative, mild preparative route to Si-based functional materials with preserved morphology and components of the Si-precursors.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"41 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142911568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bao-Ngan Nguyen-Ha, Nguyen Minh Tam, Pham-Ho My-Phuong, Minh T. Nguyen
Abstract A theoretical investigation, employing density functional theory with the PBE functional and the Def2-TZVP basis set, comprehensively explores the geometric and electronic structures and properties of the boron doped scandium clusters BmScn-m+/0 with m = 2-3 and n = 3-13. Introduction of B atoms significantly enhances the stability of resulting clusters with respect to initial counterparts. As the number of B atoms increases, the stability of the doped clusters improves, following the order: B3Scn-3+/0 > B2Scn-2+/0 > BScn-1+/0 > Scn+/0. Notably, the B2@Sc8 cluster represents the smallest fully endohedral doubly doped cage, and the B3@Sc10 is the smallest fully endohedral triply doped cage reported to date. The size with 8 Sc atoms plays a crucial role in the structural evolution of both doubly doped B2Scn-2+/0 and triply doped B3Scn-3+/0 series. For the doubly doped species, this size marks an exohedral-to-endohedral transition, while in the triply doped species, it marks an interconversion of B3 dopant from a triangular to a linear arrangement. In the triangular B3 trimer, the electron and charge distribution are evenly shared among the three B atoms, whereas in the linear B3 trimer, these distributions are unequal. Additionally, the geometric and electronic structure of the linear-B3 doped B3@Sc8 can serve as a basic building block for the construction of larger clusters.
{"title":"Endohedral Boron-doped Scandium Clusters BmScn-m+/0 (m = 2 – 3, n = 3-13): Triangular - Linear Rearrangement of the B3 Dopant","authors":"Bao-Ngan Nguyen-Ha, Nguyen Minh Tam, Pham-Ho My-Phuong, Minh T. Nguyen","doi":"10.1039/d4dt03054k","DOIUrl":"https://doi.org/10.1039/d4dt03054k","url":null,"abstract":"Abstract A theoretical investigation, employing density functional theory with the PBE functional and the Def2-TZVP basis set, comprehensively explores the geometric and electronic structures and properties of the boron doped scandium clusters BmScn-m+/0 with m = 2-3 and n = 3-13. Introduction of B atoms significantly enhances the stability of resulting clusters with respect to initial counterparts. As the number of B atoms increases, the stability of the doped clusters improves, following the order: B3Scn-3+/0 > B2Scn-2+/0 > BScn-1+/0 > Scn+/0. Notably, the B2@Sc8 cluster represents the smallest fully endohedral doubly doped cage, and the B3@Sc10 is the smallest fully endohedral triply doped cage reported to date. The size with 8 Sc atoms plays a crucial role in the structural evolution of both doubly doped B2Scn-2+/0 and triply doped B3Scn-3+/0 series. For the doubly doped species, this size marks an exohedral-to-endohedral transition, while in the triply doped species, it marks an interconversion of B3 dopant from a triangular to a linear arrangement. In the triangular B3 trimer, the electron and charge distribution are evenly shared among the three B atoms, whereas in the linear B3 trimer, these distributions are unequal. Additionally, the geometric and electronic structure of the linear-B3 doped B3@Sc8 can serve as a basic building block for the construction of larger clusters.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"16 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142911563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohammad Irfan, Ashok Jeshurun, Mallikharjuna Reddy Bogala
The existing demand for the development of innovative multimodal imaging nanomaterial probes for biomedical applications stems from their unique combination of dual response modalities, i.e., photoluminescence (PL) and magnetic resonance imaging (MRI). In this study, for the first time, neodymium (Nd3+) and dysprosium (Dy3+) rare earth (RE) metal ions were co-doped into hydroxyapatite (HAp) crystal lattice using a simple microwave-assisted synthesis technique to incorporate the essential properties of both the lanthanides in HAp. Theoretical as well as experimental studies were performed on novel Nd:Dy:HAp nanoparticles (NPs) to understand its photoluminescence and magnetic behaviour. Through co-precipitation, RE (Nd3+, Dy3+) ions were effectively integrated into the HAp crystal lattice, where they preferentially occupy the calcium ion (Ca2+) sites. The as-synthesized HAp, Nd:HAp, Dy:HAp, and Nd:Dy:HAp samples were characterized using different analytical tools. The PL and magnetic characteristics of Nd:Dy:HAp, are dependent on the RE dopant ion type and concentration. In comparison to the pure HAp, the RE co-doped (Nd:Dy:HAp) NPs displayed multimodal features due to efficient energy transfer from the Nd3+ (sensitizer) to the Dy3+ (activator) ions. Furthermore, Nd:Dy:HAp NPs have good antimicrobial properties and they also displayed low cell toxicity effects. Hence, Nd:Dy:HAp NPs are attractive biomaterials for PL and MRI applications (e.g. permanent bone and tooth implants) and they can effectively be utilized in biomedical industry for target-specific drug delivery, bioimaging, functional antimicrobial coatings etc due to their tunable PL, magnetic, antimicrobial, and biocompatible capabilities.
{"title":"Microwave-assisted synthesis of dual responsive luminomagnetic rare earth metal ions (Nd3+, Dy3+) co-doped nanohydroxyapatite for biomedical applications","authors":"Mohammad Irfan, Ashok Jeshurun, Mallikharjuna Reddy Bogala","doi":"10.1039/d4dt02664k","DOIUrl":"https://doi.org/10.1039/d4dt02664k","url":null,"abstract":"The existing demand for the development of innovative multimodal imaging nanomaterial probes for biomedical applications stems from their unique combination of dual response modalities, i.e., photoluminescence (PL) and magnetic resonance imaging (MRI). In this study, for the first time, neodymium (Nd3+) and dysprosium (Dy3+) rare earth (RE) metal ions were co-doped into hydroxyapatite (HAp) crystal lattice using a simple microwave-assisted synthesis technique to incorporate the essential properties of both the lanthanides in HAp. Theoretical as well as experimental studies were performed on novel Nd:Dy:HAp nanoparticles (NPs) to understand its photoluminescence and magnetic behaviour. Through co-precipitation, RE (Nd3+, Dy3+) ions were effectively integrated into the HAp crystal lattice, where they preferentially occupy the calcium ion (Ca2+) sites. The as-synthesized HAp, Nd:HAp, Dy:HAp, and Nd:Dy:HAp samples were characterized using different analytical tools. The PL and magnetic characteristics of Nd:Dy:HAp, are dependent on the RE dopant ion type and concentration. In comparison to the pure HAp, the RE co-doped (Nd:Dy:HAp) NPs displayed multimodal features due to efficient energy transfer from the Nd3+ (sensitizer) to the Dy3+ (activator) ions. Furthermore, Nd:Dy:HAp NPs have good antimicrobial properties and they also displayed low cell toxicity effects. Hence, Nd:Dy:HAp NPs are attractive biomaterials for PL and MRI applications (e.g. permanent bone and tooth implants) and they can effectively be utilized in biomedical industry for target-specific drug delivery, bioimaging, functional antimicrobial coatings etc due to their tunable PL, magnetic, antimicrobial, and biocompatible capabilities.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"14 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142911569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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