Isabel José Romero-Castellón, Lenka Markova, María José Piernas-Muñoz, Hana Kostrhunova, Jana Kasparkova, Christoph Janiak, Marta Erminia Alberto, Antonio Francés-Monerris, Jose Ruiz, Viktor Brabec
Eight novel arylterpyridine iridium(III) complexes [Ir(N^N^N)(C^N)Cl]PF6 (Ir1-Ir8), incorporating diverse para-substituents and extended aromatic groups, were synthesized and fully characterized. Upon exposure to biocompatible blue light, all complexes demonstrated potent antiproliferative effects in both 2D and 3D cancer cell models, with minimal toxicity toward non-cancerous cells. Complexes Ir2, Ir3, and Ir8 -those containing 9-anthracenyl-, 1,3benzodioxole-5-yl substituents, and 1,4-benzodioxan-6-yl, respectively -displayed the highest phototoxic indices and were further investigated. Ir2 and Ir3 preferentially localized in the cytoplasm of HCT116 cells, inducing oncotic-like cell death upon irradiation, characterized by distinct cellular morphological changes, adenosine triphosphate (ATP) depletion, and porimin upregulation. Mechanistic studies revealed that photoactivated Ir2 and Ir3 catalyzed nicotinamide adenine dinucleotide (NADH) oxidation with high turnover frequencies, accompanied by the generation of reactive oxygen species (ROS). Molecular dynamics and hybrid QM/MM simulations supported the formation of non-covalent Ir-NADH heterodimers, with Mulliken charge analysis indicating NADH→Ir charge transfer stabilized triplet states and identifying Ir8 as the most efficient NADH photocatalyst, in agreement with experimental evidence obtained by intracellular NAD⁺/NADH assays. Collectively, these findings establish a mechanistic framework for a novel class of photoactivated iridium complexes that exert synergistic phototoxic and photocatalytic effects, offering a promising alternative to conventional ROS-driven photodynamic therapy.
{"title":"Photocatalytic arylterpyridine iridium(III) complexes trigger oncosis in 2D and 3D cancer cell models via NADH oxidation","authors":"Isabel José Romero-Castellón, Lenka Markova, María José Piernas-Muñoz, Hana Kostrhunova, Jana Kasparkova, Christoph Janiak, Marta Erminia Alberto, Antonio Francés-Monerris, Jose Ruiz, Viktor Brabec","doi":"10.1039/d5qi02205c","DOIUrl":"https://doi.org/10.1039/d5qi02205c","url":null,"abstract":"Eight novel arylterpyridine iridium(III) complexes [Ir(N^N^N)(C^N)Cl]PF6 (Ir1-Ir8), incorporating diverse para-substituents and extended aromatic groups, were synthesized and fully characterized. Upon exposure to biocompatible blue light, all complexes demonstrated potent antiproliferative effects in both 2D and 3D cancer cell models, with minimal toxicity toward non-cancerous cells. Complexes Ir2, Ir3, and Ir8 -those containing 9-anthracenyl-, 1,3benzodioxole-5-yl substituents, and 1,4-benzodioxan-6-yl, respectively -displayed the highest phototoxic indices and were further investigated. Ir2 and Ir3 preferentially localized in the cytoplasm of HCT116 cells, inducing oncotic-like cell death upon irradiation, characterized by distinct cellular morphological changes, adenosine triphosphate (ATP) depletion, and porimin upregulation. Mechanistic studies revealed that photoactivated Ir2 and Ir3 catalyzed nicotinamide adenine dinucleotide (NADH) oxidation with high turnover frequencies, accompanied by the generation of reactive oxygen species (ROS). Molecular dynamics and hybrid QM/MM simulations supported the formation of non-covalent Ir-NADH heterodimers, with Mulliken charge analysis indicating NADH→Ir charge transfer stabilized triplet states and identifying Ir8 as the most efficient NADH photocatalyst, in agreement with experimental evidence obtained by intracellular NAD⁺/NADH assays. Collectively, these findings establish a mechanistic framework for a novel class of photoactivated iridium complexes that exert synergistic phototoxic and photocatalytic effects, offering a promising alternative to conventional ROS-driven photodynamic therapy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yongwoo Jeon, Hong Gu Kang, Seohee Park, Younghyun Kim, Seong-Yong Cho, Dennis Lee, Younghoon Kim, Sung Nam Lim, Byeong Guk Jeong, Sohee Jeong, Jung Hoon Song, Ju Young Woo
Performance of colloidal quantum dot (QD) solar cells usually employing PbS QDs are fundamentally limited by short carrier diffusion lengths that originate from inter-dot hopping transport. This limitation prevents the use of thick absorber layers required for complete light harvesting and suppresses power conversion efficiency. Here, we report ternary PbSeS QDs engineered to simultaneously retain a near-optimal single-junction bandgap and enhance charge transport. Controlled incorporation of selenium through tailored anion precursor chemistry enables uniform alloying while maintaining absorption peaks near 930 nm, close to the Shockley-Queisser optimal band gap. Space-charge-limited current analysis reveals that ternary PbSeS QDs exhibit substantially higher carrier mobilities, showing 3.8× and 2.3× improvements in electron and hole transport compared to PbS QDs, respectively. Devices studies using fully depleted architectures confirm that the mobility enhancement improves solar cell performance by suppressing carrier recombination in the depletion region. Furthermore, the extended diffusion length enables the fabrication of thicker QD absorbers, allowing PbSeS QD solar cells to maintain high efficiency even with active layers up to ~500 nm, while conventional binary PbS QD solar cells suffer performance degradation with thick QD absorbers. The results establish ternary PbSeS QDs as a robust platform for overcoming the diffusion length bottleneck in QD photovoltaics, enabling efficient devices with thicker lightabsorbing layers.
{"title":"Enhanced Carrier Mobility-Driven Performance Improvement in Colloidal Quantum Dot Solar Cells","authors":"Yongwoo Jeon, Hong Gu Kang, Seohee Park, Younghyun Kim, Seong-Yong Cho, Dennis Lee, Younghoon Kim, Sung Nam Lim, Byeong Guk Jeong, Sohee Jeong, Jung Hoon Song, Ju Young Woo","doi":"10.1039/d5qi02004b","DOIUrl":"https://doi.org/10.1039/d5qi02004b","url":null,"abstract":"Performance of colloidal quantum dot (QD) solar cells usually employing PbS QDs are fundamentally limited by short carrier diffusion lengths that originate from inter-dot hopping transport. This limitation prevents the use of thick absorber layers required for complete light harvesting and suppresses power conversion efficiency. Here, we report ternary PbSeS QDs engineered to simultaneously retain a near-optimal single-junction bandgap and enhance charge transport. Controlled incorporation of selenium through tailored anion precursor chemistry enables uniform alloying while maintaining absorption peaks near 930 nm, close to the Shockley-Queisser optimal band gap. Space-charge-limited current analysis reveals that ternary PbSeS QDs exhibit substantially higher carrier mobilities, showing 3.8× and 2.3× improvements in electron and hole transport compared to PbS QDs, respectively. Devices studies using fully depleted architectures confirm that the mobility enhancement improves solar cell performance by suppressing carrier recombination in the depletion region. Furthermore, the extended diffusion length enables the fabrication of thicker QD absorbers, allowing PbSeS QD solar cells to maintain high efficiency even with active layers up to ~500 nm, while conventional binary PbS QD solar cells suffer performance degradation with thick QD absorbers. The results establish ternary PbSeS QDs as a robust platform for overcoming the diffusion length bottleneck in QD photovoltaics, enabling efficient devices with thicker lightabsorbing layers.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sergey Kutumov, Dmitry Kholodkov, Irina K Goncharova, Anna V. V. Vologzhanina, Alexander D. Volodin, Alexander Korlyukov, Pavel Dorovatovskii, Alexey S. Kashin, Roman A Novikov, Valery Vlasenko, Ilia A. Pankin, Alexander A. Guda, Ashot V Arzumanyan
The use of the organosiloxane compound, all-cis-tetra(p-carboxyphenyl)-cyclotetrasiloxane (A) as a ligand for the construction of MOFs was studied. A has a stereoregular cyclic structure and amphiphilic nature due to 4 hydrophilic carboxyl and 4 hydrophobic trimethylsiloxy groups attached to the opposite sides of the cyclosiloxane. In spite of the well-defined configuration of A, the flexible organosiloxane skeleton allows the ligand to adopt various conformations, as illustrated by obtaining a large family of crystalline MOFs (10 examples). The structural features of these organosiloxane MOFs were studied in depth using a combination of analytic physical methods (SCXRD, PXRD, MAS SSNMR, XAS, SEM, TEM, etc.) using Cu-containing MOF (B) as an example. Then, using acquired understanding, amorphous Cu-containing MOFs, with metal-organic aerogel (MOA) being the brightest example, were obtained. Its structure was confirmed by comparison with the well-defined structure of MOF B and other related products. MOA has a very low density (0.01 g/mL) and a moderate specific surface area, as well as being highly hydrophobic, chemically and thermally stable. For example, MOA could be used as an active and recyclable catalyst for C–N cross-coupling and aerobic oxidation. In addition, it can be evenly dispersed in a hydrophobic matrix (PDMS), allowing it to overcome challenges in obtaining homogeneous and isotropic monoliths. Due to the mobile organosiloxane skeleton of the ligand А, it is possible to obtain breathing and stimulus-responsive materials, e.g., repeatedly recyclable (at least 60 times) moisture indicators. Another important advantage is the resource- and energy efficiency of both A (in just two key synthetic steps under mild conditions and using inexpensive and commercially available reagents) and A-based MOFs (at room temperature, 1 atm, air) synthesis. These results demonstrate the high potential of stereoregular cyclic organosiloxane ligands for designing CP and MOF structures and the creation of a new-generation of stable, multifunctional, and smart hybrid materials.
{"title":"Crystalline and Amorphous MOFs Based on an Amphiphilic Cyclic Stereoregular p-Carboxyphenylsiloxane: Synthesis, Structures and Properties","authors":"Sergey Kutumov, Dmitry Kholodkov, Irina K Goncharova, Anna V. V. Vologzhanina, Alexander D. Volodin, Alexander Korlyukov, Pavel Dorovatovskii, Alexey S. Kashin, Roman A Novikov, Valery Vlasenko, Ilia A. Pankin, Alexander A. Guda, Ashot V Arzumanyan","doi":"10.1039/d5qi02173a","DOIUrl":"https://doi.org/10.1039/d5qi02173a","url":null,"abstract":"The use of the organosiloxane compound, all-cis-tetra(p-carboxyphenyl)-cyclotetrasiloxane (A) as a ligand for the construction of MOFs was studied. A has a stereoregular cyclic structure and amphiphilic nature due to 4 hydrophilic carboxyl and 4 hydrophobic trimethylsiloxy groups attached to the opposite sides of the cyclosiloxane. In spite of the well-defined configuration of A, the flexible organosiloxane skeleton allows the ligand to adopt various conformations, as illustrated by obtaining a large family of crystalline MOFs (10 examples). The structural features of these organosiloxane MOFs were studied in depth using a combination of analytic physical methods (SCXRD, PXRD, MAS SSNMR, XAS, SEM, TEM, etc.) using Cu-containing MOF (B) as an example. Then, using acquired understanding, amorphous Cu-containing MOFs, with metal-organic aerogel (MOA) being the brightest example, were obtained. Its structure was confirmed by comparison with the well-defined structure of MOF B and other related products. MOA has a very low density (0.01 g/mL) and a moderate specific surface area, as well as being highly hydrophobic, chemically and thermally stable. For example, MOA could be used as an active and recyclable catalyst for C–N cross-coupling and aerobic oxidation. In addition, it can be evenly dispersed in a hydrophobic matrix (PDMS), allowing it to overcome challenges in obtaining homogeneous and isotropic monoliths. Due to the mobile organosiloxane skeleton of the ligand А, it is possible to obtain breathing and stimulus-responsive materials, e.g., repeatedly recyclable (at least 60 times) moisture indicators. Another important advantage is the resource- and energy efficiency of both A (in just two key synthetic steps under mild conditions and using inexpensive and commercially available reagents) and A-based MOFs (at room temperature, 1 atm, air) synthesis. These results demonstrate the high potential of stereoregular cyclic organosiloxane ligands for designing CP and MOF structures and the creation of a new-generation of stable, multifunctional, and smart hybrid materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"251 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photocatalysis offers an effective approach for the treatment of refractory tetracycline (TC) contamination. Conventional TiO2-based semiconductor photocatalysts for TC degradation are limited by their narrow spectral response range and rapid electron-hole recombination. In this study, ternary Bi2MoO6/graphene quantum dots/TiO2 nanotube arrays (BGT) photocatalysts with dual Z-scheme heterojunctions were designed and synthesized to overcome these limitations. The removal efficiency of TC by BGT-2 photocatalysts in photoelectrocatalytic degradation reached 79.72% within 120 minutes, with an enhanced apparent reaction rate constant (Kapp= 13.62×10-3 min-1), representing a 2.41-fold enhancement compared to TiO2 (5.65×10-3 min-1). The optimized photocatalyst, BGT-2, exhibited a photocurrent density of 9.96 μA cm-2 and a carrier density of 7.18×1020 cm-3, demonstrating high charge separation efficiency. This enhanced photoelectrochemical performance was attributed to the formation of dual Z-scheme heterojunctions, which maintain the strong redox potentials of photogenerated carriers and reduce recombination losses. This work presents a novel material construction strategy for developing high-performance photocatalysts to address persistent antibiotic contamination.
{"title":"Visible-Light-Driven Photoelectrocatalytic Degradation of Tetracycline Using Dual Z-Scheme Bi2MoO6/GQDs/TiO2 Heterojunctions","authors":"Feiyu Li, Kailu Liu, Hanyue Zhang, Xing Wang, Jingui Ma, Yansheng Liu, Junwei Hou","doi":"10.1039/d5qi02154e","DOIUrl":"https://doi.org/10.1039/d5qi02154e","url":null,"abstract":"Photocatalysis offers an effective approach for the treatment of refractory tetracycline (TC) contamination. Conventional TiO2-based semiconductor photocatalysts for TC degradation are limited by their narrow spectral response range and rapid electron-hole recombination. In this study, ternary Bi2MoO6/graphene quantum dots/TiO2 nanotube arrays (BGT) photocatalysts with dual Z-scheme heterojunctions were designed and synthesized to overcome these limitations. The removal efficiency of TC by BGT-2 photocatalysts in photoelectrocatalytic degradation reached 79.72% within 120 minutes, with an enhanced apparent reaction rate constant (Kapp= 13.62×10-3 min-1), representing a 2.41-fold enhancement compared to TiO2 (5.65×10-3 min-1). The optimized photocatalyst, BGT-2, exhibited a photocurrent density of 9.96 μA cm-2 and a carrier density of 7.18×1020 cm-3, demonstrating high charge separation efficiency. This enhanced photoelectrochemical performance was attributed to the formation of dual Z-scheme heterojunctions, which maintain the strong redox potentials of photogenerated carriers and reduce recombination losses. This work presents a novel material construction strategy for developing high-performance photocatalysts to address persistent antibiotic contamination.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"47 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Toxic and carcinogenic organic pollutants in wastewater severely threaten public health and environmental sustainability. Advanced oxidation processes (AOPs) can degrade such pollutants by generating highly reactive species, but their efficiency and durability depend heavily on the reaction pathways and mechanisms. Non-radical pathways offer notable advantages for complex wastewater due to their strong resistance to interference from impurities and coexisting ions. Herein, we demonstrate that the entropy can drive a transition in the peroxymonosulfate (PMS) activation mechanism from free-radical- to non-radical-dominated pathway. This is exemplified by the Co55Fe15Cu10Mn10Ni10 high-entropy alloy (HEA), which achieves over 98% degradation of Rhodamine B within 15 minutes using a low PMS dosage of 0.15 g/L, significantly outperforming monometallic and binary alloy catalysts. The non-radical mechanism combined with high structural stability of HEA catalysts also grants exceptional resistance to coexisting ions and reliable performance in real water samples with multiple impurities. These findings highlight the promise of HEA catalysts in addressing key challenges in wastewater treatment, including pollutant diversity, impurity resilience, and system durability.
{"title":"Non-Radical Dominated PMS Activation by High-Entropy Alloy for Water Decontamination","authors":"Youzhong Hu, Jinli Chen, Hanwen Liu, Wenhui Shi, Wei Wang, Fatang Tan, Xiaodong Chi, Yonggang Yao","doi":"10.1039/d5qi02164b","DOIUrl":"https://doi.org/10.1039/d5qi02164b","url":null,"abstract":"Toxic and carcinogenic organic pollutants in wastewater severely threaten public health and environmental sustainability. Advanced oxidation processes (AOPs) can degrade such pollutants by generating highly reactive species, but their efficiency and durability depend heavily on the reaction pathways and mechanisms. Non-radical pathways offer notable advantages for complex wastewater due to their strong resistance to interference from impurities and coexisting ions. Herein, we demonstrate that the entropy can drive a transition in the peroxymonosulfate (PMS) activation mechanism from free-radical- to non-radical-dominated pathway. This is exemplified by the Co55Fe15Cu10Mn10Ni10 high-entropy alloy (HEA), which achieves over 98% degradation of Rhodamine B within 15 minutes using a low PMS dosage of 0.15 g/L, significantly outperforming monometallic and binary alloy catalysts. The non-radical mechanism combined with high structural stability of HEA catalysts also grants exceptional resistance to coexisting ions and reliable performance in real water samples with multiple impurities. These findings highlight the promise of HEA catalysts in addressing key challenges in wastewater treatment, including pollutant diversity, impurity resilience, and system durability.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The utilization of solar photocatalytic oxidation technology represents an effective strategy for addressing environmental pollution and energy shortages. To effectively treat nitro pollutants in wastewater from the explosive industries, a novel composite catalyst H 200 ZIF-8/TiO 2 was proposed with an extended visible light corresponding range and enhanced photogenerated carrier utilization. The optimized photocatalytic reaction conditions are determined to be a pH of 4, with the NaBH 4 dosage of 1 mL at 25 mg mL -1 , and the catalyst dosage of 200 mg L -1 . Under these conditions, the reduction rate of TNP by H 200 ZIF-8/TiO 2 achieves a value of 98.44% within 10 min.The rate constant of 0.412 min -1 is 5.2 times greater than that of TiO 2 and 3.0 times than that of H 200 ZIF-8, demonstrating excellent photocatalytic performance.Characterization of the photoelectric properties and theoretical calculations confirm that the construction of heterojunctions effectively enhances the separation of photogenerated carriers, and based on these, a possible reaction mechanism is put forward. This study offers a novel idea for the design of ZIF-8-based heterojunction photocatalysts, and its high efficiency and green characteristics show broad application prospects in the treatment of wastewater containing nitro explosives.
利用太阳能光催化氧化技术是解决环境污染和能源短缺的有效策略。为了有效处理爆炸工业废水中的硝基污染物，提出了一种新型复合催化剂H 200 ZIF-8/ tio2，该催化剂具有扩大可见光对应范围和提高光生载体利用率的特点。优化后的光催化反应条件为pH = 4， nabh4用量为1 mL， 25 mg mL -1，催化剂用量为200 mg L -1。在此条件下，h200 ZIF-8/ tio2在10 min内对TNP的还原率达到98.44%。反应速率常数为0.412 min -1，是tio2的5.2倍，是h200 ZIF-8的3.0倍，表现出优异的光催化性能。光电性质表征和理论计算证实异质结的构建有效地增强了光生载流子的分离，并在此基础上提出了一种可能的反应机理。本研究为zif -8基异质结光催化剂的设计提供了新的思路，其高效、绿色的特性在处理硝基炸药废水中具有广阔的应用前景。
{"title":"HxZIF-8/TiO2 with Step-Scheme Heterojunction for Visible-Light Photocatalytic Reduction of Nitroaromatic Explosives","authors":"Yuji Zhou, Jiaojiao Zhang, Yongjie Zhao, Lili Qiu","doi":"10.1039/d5qi02222c","DOIUrl":"https://doi.org/10.1039/d5qi02222c","url":null,"abstract":"The utilization of solar photocatalytic oxidation technology represents an effective strategy for addressing environmental pollution and energy shortages. To effectively treat nitro pollutants in wastewater from the explosive industries, a novel composite catalyst H 200 ZIF-8/TiO 2 was proposed with an extended visible light corresponding range and enhanced photogenerated carrier utilization. The optimized photocatalytic reaction conditions are determined to be a pH of 4, with the NaBH 4 dosage of 1 mL at 25 mg mL -1 , and the catalyst dosage of 200 mg L -1 . Under these conditions, the reduction rate of TNP by H 200 ZIF-8/TiO 2 achieves a value of 98.44% within 10 min.The rate constant of 0.412 min -1 is 5.2 times greater than that of TiO 2 and 3.0 times than that of H 200 ZIF-8, demonstrating excellent photocatalytic performance.Characterization of the photoelectric properties and theoretical calculations confirm that the construction of heterojunctions effectively enhances the separation of photogenerated carriers, and based on these, a possible reaction mechanism is put forward. This study offers a novel idea for the design of ZIF-8-based heterojunction photocatalysts, and its high efficiency and green characteristics show broad application prospects in the treatment of wastewater containing nitro explosives.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
With the increasing demand for noncontact thermometry, optical thermometers have garnered intense interest. With this end in view, Bi3+-doped BaYScO4 and BaGdScO4 phosphors were prepared via a high-temperature solid-state method in this work. Under near-ultraviolet excitation, the two phosphors exhibit broad-band yellow and orange luminescence, respectively, originating from Bi3+-Sc3+ MMCT transitions. Their luminescence manifests strong temperature dependence. Above 200 K, the emission intensity decreases rapidly with increasing temperature, yielding a maximum relative sensitivity (S_r) exceeding 2% for temperature sensing based on luminescence intensity. Moreover, across the broad temperature range of 60 – 420 K, the fluorescence lifetime shortens markedly as temperature increases. In terms of the temperature-dependent lifetime, the S_r value consistently stays above 0.77%. In the low-temperature region (60 – 210 K), the maximum S_r values are 4.40% for BaYScO4: Bi³⁺ and 2.31% for BaGdScO4: Bi³⁺. At higher temperatures (210 – 420 K), their maximum S_r values are 2.23% and 2.34%, respectively. Owing to the sharp lifetime decrease of BaGdScO4: 0.02Bi3+ near room temperature, a temperature-sensing strategy based on the time-resolved technique is implemented. Temperature calibration is accomplished by measuring the ratio of integrated emission intensities within two specific time windows in the fluorescence decay process at different temperatures. This method results in a high performance of S_r that increased from 1.77% K⁻¹ to 3.01% K⁻¹ between 300 and 345 K. Finally, to validate the feasibility of this strategy, temperature imaging on a printed circuit board is successfully demonstrated using an ICCD camera coupled with a fluorescence microscope. These results collectively indicate that the fluorescence intensity and lifetime of both BaYScO4: Bi3+ and BaGdScO4: Bi3+ are highly temperature-sensitive, promising their great potential for applications in optical thermometry and thermal imaging.
{"title":"Bi3+-doped BaMScO4 (M = Y, Gd) phosphors as multiple-mode optical thermometer for potential applications in optical thermometry and temperature imaging","authors":"Zhicheng Liao, Qian Zhang, Xiantao Wei, Liting Qiu, Yonghu Chen, Min Yin","doi":"10.1039/d5qi02292d","DOIUrl":"https://doi.org/10.1039/d5qi02292d","url":null,"abstract":"With the increasing demand for noncontact thermometry, optical thermometers have garnered intense interest. With this end in view, Bi3+-doped BaYScO4 and BaGdScO4 phosphors were prepared via a high-temperature solid-state method in this work. Under near-ultraviolet excitation, the two phosphors exhibit broad-band yellow and orange luminescence, respectively, originating from Bi3+-Sc3+ MMCT transitions. Their luminescence manifests strong temperature dependence. Above 200 K, the emission intensity decreases rapidly with increasing temperature, yielding a maximum relative sensitivity (S_r) exceeding 2% for temperature sensing based on luminescence intensity. Moreover, across the broad temperature range of 60 – 420 K, the fluorescence lifetime shortens markedly as temperature increases. In terms of the temperature-dependent lifetime, the S_r value consistently stays above 0.77%. In the low-temperature region (60 – 210 K), the maximum S_r values are 4.40% for BaYScO4: Bi³⁺ and 2.31% for BaGdScO4: Bi³⁺. At higher temperatures (210 – 420 K), their maximum S_r values are 2.23% and 2.34%, respectively. Owing to the sharp lifetime decrease of BaGdScO4: 0.02Bi3+ near room temperature, a temperature-sensing strategy based on the time-resolved technique is implemented. Temperature calibration is accomplished by measuring the ratio of integrated emission intensities within two specific time windows in the fluorescence decay process at different temperatures. This method results in a high performance of S_r that increased from 1.77% K⁻¹ to 3.01% K⁻¹ between 300 and 345 K. Finally, to validate the feasibility of this strategy, temperature imaging on a printed circuit board is successfully demonstrated using an ICCD camera coupled with a fluorescence microscope. These results collectively indicate that the fluorescence intensity and lifetime of both BaYScO4: Bi3+ and BaGdScO4: Bi3+ are highly temperature-sensitive, promising their great potential for applications in optical thermometry and thermal imaging.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Artificial micro/nanowires derived from coordination polymers (CPs) are highly attractive due to their unique physicochemical properties; however, their stability in solution has remained a significant challenge. Herein we propose an innovative strategy, i.e., enhancing their stability in solvents by forming CP superhelix structures. The study focuses on the chiral lanthanide phosphonate compounds, specifically R- and S-Dy(pempH)3·H2O with one-dimensional (1D) chain structures, which can exist in both crystalline (R-, S-1c) and helical forms (R-, S-1h). We initially assessed the stability of R-1c crystals immersed in various solvents. At ambient conditions, R-1c crystals proved stable in water but swelled to varying extents when exposed to alkyl alcohol (MeOH, EtOH, n-PrOH, n-BuOH), and quickly exfoliated in halomethane (CH2Cl2, CHCl3, CH2Br2, CHBr3) to form gels. All-atom molecular dynamics simulations indicated that solvent-chain interactions, solvent-solvent interactions, and the size of solvent molecules collectively influence the swelling or striping rate of R-1c crystals. Interestingly, chiral aerogels obtained by supercritical carbon dioxide treatment of the R-1c gels formed in CHCl3 (12.0 mmol/L) exhibited enantioselective adsorption properties toward chiral molecules of R- and S-2-butanol. Moreover, after a 2 min dispersion in a dilute CHCl3 solution of R-1c (0.12 mmol/L), ultralong nanowires of R-1nw were produced, which fragmented into nanoparticles within 10 min of dispersion. In contrast, the R-1h superhelix remained stable within 10 min in the same dilute CHCl3 solution. These findings suggest that the formation of helical structures enhances interchain interactions, significantly improving the stability of 1D CP micro/nanowires in solvents. This research may provide valuable insights for developing functional CP micro/nanowires for practical applications.
{"title":"The helical structure enhances the stability of a chiral one-dimensional dysprosium phosphonate in solvent","authors":"Zhi-Min Zhai, Zeng-shuai Yan, Yan Xu, Yaoyao Zhang, Tinglian Yuan, Hong-Ming Ding, Song-Song Bao, Yu-Qiang Ma, Wei Wang, Li-Min Zheng","doi":"10.1039/d5qi02315g","DOIUrl":"https://doi.org/10.1039/d5qi02315g","url":null,"abstract":"Artificial micro/nanowires derived from coordination polymers (CPs) are highly attractive due to their unique physicochemical properties; however, their stability in solution has remained a significant challenge. Herein we propose an innovative strategy, i.e., enhancing their stability in solvents by forming CP superhelix structures. The study focuses on the chiral lanthanide phosphonate compounds, specifically R- and S-Dy(pempH)3·H2O with one-dimensional (1D) chain structures, which can exist in both crystalline (R-, S-1c) and helical forms (R-, S-1h). We initially assessed the stability of R-1c crystals immersed in various solvents. At ambient conditions, R-1c crystals proved stable in water but swelled to varying extents when exposed to alkyl alcohol (MeOH, EtOH, n-PrOH, n-BuOH), and quickly exfoliated in halomethane (CH2Cl2, CHCl3, CH2Br2, CHBr3) to form gels. All-atom molecular dynamics simulations indicated that solvent-chain interactions, solvent-solvent interactions, and the size of solvent molecules collectively influence the swelling or striping rate of R-1c crystals. Interestingly, chiral aerogels obtained by supercritical carbon dioxide treatment of the R-1c gels formed in CHCl3 (12.0 mmol/L) exhibited enantioselective adsorption properties toward chiral molecules of R- and S-2-butanol. Moreover, after a 2 min dispersion in a dilute CHCl3 solution of R-1c (0.12 mmol/L), ultralong nanowires of R-1nw were produced, which fragmented into nanoparticles within 10 min of dispersion. In contrast, the R-1h superhelix remained stable within 10 min in the same dilute CHCl3 solution. These findings suggest that the formation of helical structures enhances interchain interactions, significantly improving the stability of 1D CP micro/nanowires in solvents. This research may provide valuable insights for developing functional CP micro/nanowires for practical applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zachary Warren, Thomas Poupeau, Beyza Batu, Nataly Carolina Rosero-Navarro
All-solid-state lithium batteries benefit from scalable routes to sulfide solid electrolytes with controlled phase formation. Here, an in situ Raman spectrometer integrated with a microwave reactor provides real-time vibrational fingerprints of the liquid-phase reaction between Li2S and P4S10 in acetonitrile. We benchmark the cell by tracking P4S10 solubility up to 130 °C and establish analytical performance for the PS stretch at ∼716 cm−1, determining LOD = 0.78 mM and LOQ = 2.60 mM. Time-resolved spectra capture the systematic decay of the 716 cm−1 band during the reaction, consistent with the disruption of the P4S10 cage and formation of thiophosphate intermediates. Early-stage kinetics are quantitatively described by the Finke–Watzky two-step model, and temperature-dependent rate constants yield Arrhenius and Eyring relationships with Ea(mw) = 39.59 kJ mol−1, ΔH‡ = 36.97 kJ mol−1, and ΔS‡ = −178.55 J mol−1 K−1. This combined in situ spectroscopic–kinetic approach offers a direct pathway to mechanistic understanding and parameter extraction in solution-based synthesis of sulfide SSEs.
{"title":"Real-time vibrational fingerprinting of liquid-phase sulfide electrolyte synthesis via in situ Raman spectroscopy","authors":"Zachary Warren, Thomas Poupeau, Beyza Batu, Nataly Carolina Rosero-Navarro","doi":"10.1039/d5qi01971k","DOIUrl":"https://doi.org/10.1039/d5qi01971k","url":null,"abstract":"All-solid-state lithium batteries benefit from scalable routes to sulfide solid electrolytes with controlled phase formation. Here, an <em>in situ</em> Raman spectrometer integrated with a microwave reactor provides real-time vibrational fingerprints of the liquid-phase reaction between Li<small><sub>2</sub></small>S and P<small><sub>4</sub></small>S<small><sub>10</sub></small> in acetonitrile. We benchmark the cell by tracking P<small><sub>4</sub></small>S<small><sub>10</sub></small> solubility up to 130 °C and establish analytical performance for the P<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>S stretch at ∼716 cm<small><sup>−1</sup></small>, determining LOD = 0.78 mM and LOQ = 2.60 mM. Time-resolved spectra capture the systematic decay of the 716 cm<small><sup>−1</sup></small> band during the reaction, consistent with the disruption of the P<small><sub>4</sub></small>S<small><sub>10</sub></small> cage and formation of thiophosphate intermediates. Early-stage kinetics are quantitatively described by the Finke–Watzky two-step model, and temperature-dependent rate constants yield Arrhenius and Eyring relationships with <em>E</em><small><sub>a</sub></small>(mw) = 39.59 kJ mol<small><sup>−1</sup></small>, Δ<em>H</em><small><sup>‡</sup></small> = 36.97 kJ mol<small><sup>−1</sup></small>, and Δ<em>S</em><small><sup>‡</sup></small> = −178.55 J mol<small><sup>−1</sup></small> K<small><sup>−1</sup></small>. This combined <em>in situ</em> spectroscopic–kinetic approach offers a direct pathway to mechanistic understanding and parameter extraction in solution-based synthesis of sulfide SSEs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yao Li, Hang Li, Qianwen Guan, Huang Ye, Chengshu Zhang, Lijun Xu, Haiqing Zhong, Xinwei Zhou, Junhua Luo
Three-dimensional (3D) organic-inorganic hybrid perovskites (OIHPs) are known for excellent charge transport and large light absorption coefficients, making them promising materials for ultraviolet (UV) photodetection. However, the traditional 3D ABX3 perovskite structure is constrained by the tolerance factor, limiting its capacity to accommodate larger A-site cations.Therefore, it is necessary to explore novel 3D perovskitoids that can incorporate larger organic cations for UV photodetection.Herein, we introduced the diamine 3-methylaminopropylamine (3-MAPA) cation into the lead-iodide framework and successfully synthesized a 3D perovskitoid compound (3-MAPA)Pb2I6 (MPI). By forming extensive network of hydrogen bonds between the 3-MAPA 2+ cations and the inorganic framework, MPI effectively suppresses ion migration, thereby achieving ultralow dark-current drift of 8.184 × 10 -8 nA cm -1 s -1 V -1 . Owing to its 3D inorganic lattice, MPI exhibits high carrier mobility-lifetime product (μτ) of 2.613 × 10 -3 cm 2 V -1 s -1 . These synergistic effects of extensive hydrogen bonding and 3D leadhalide framework collectively enable stable UV photodetection under periodic 377 nm illumination with high responsivity (R ≈ 464.42 mA W -1) and detectivity (D * ≈ 4.05 × 10 12 Jones). This work establishes stable UV photodetection via 3D perovskitoid compound, expanding the candidate materials.
三维（3D）有机-无机杂化钙钛矿（OIHPs）以优异的电荷输运和大的光吸收系数而闻名，使其成为紫外（UV）光探测的有前途的材料。然而，传统的3D ABX3钙钛矿结构受到容差因子的限制，限制了其容纳更大的a位阳离子的能力。因此，有必要探索新的3D类钙钛矿，它可以包含更大的有机阳离子，用于紫外光检测。本文将二胺型3-甲基氨基丙胺（3-MAPA）阳离子引入到碘化铅骨架中，成功合成了三维类钙钛矿化合物（3-MAPA）Pb2I6 （MPI）。通过在3-MAPA 2+阳离子与无机骨架之间形成广泛的氢键网络，MPI有效抑制了离子迁移，从而实现了8.184 × 10 -8 nA cm -1 s -1 V -1的超低暗电流漂移。由于其三维无机晶格，MPI具有较高的载流子迁移寿命积（μτ）为2.613 × 10 -3 cm 2 V -1 s -1。这些广泛的氢键和三维铅卤化物框架的协同效应共同实现了在377 nm周期性照明下稳定的紫外光探测，具有高响应度（R≈464.42 mA W -1）和探测率（D *≈4.05 × 10 12 Jones）。本工作通过三维钙钛矿化合物建立了稳定的紫外光检测，扩大了候选材料。
{"title":"Dual-site Hydrogen Bonding in 3D Hybrid Halide Perovskitoid Towards Stable and Sensitive Ultraviolet Light Detection","authors":"Yao Li, Hang Li, Qianwen Guan, Huang Ye, Chengshu Zhang, Lijun Xu, Haiqing Zhong, Xinwei Zhou, Junhua Luo","doi":"10.1039/d5qi02302e","DOIUrl":"https://doi.org/10.1039/d5qi02302e","url":null,"abstract":"Three-dimensional (3D) organic-inorganic hybrid perovskites (OIHPs) are known for excellent charge transport and large light absorption coefficients, making them promising materials for ultraviolet (UV) photodetection. However, the traditional 3D ABX3 perovskite structure is constrained by the tolerance factor, limiting its capacity to accommodate larger A-site cations.Therefore, it is necessary to explore novel 3D perovskitoids that can incorporate larger organic cations for UV photodetection.Herein, we introduced the diamine 3-methylaminopropylamine (3-MAPA) cation into the lead-iodide framework and successfully synthesized a 3D perovskitoid compound (3-MAPA)Pb2I6 (MPI). By forming extensive network of hydrogen bonds between the 3-MAPA 2+ cations and the inorganic framework, MPI effectively suppresses ion migration, thereby achieving ultralow dark-current drift of 8.184 × 10 -8 nA cm -1 s -1 V -1 . Owing to its 3D inorganic lattice, MPI exhibits high carrier mobility-lifetime product (μτ) of 2.613 × 10 -3 cm 2 V -1 s -1 . These synergistic effects of extensive hydrogen bonding and 3D leadhalide framework collectively enable stable UV photodetection under periodic 377 nm illumination with high responsivity (R ≈ 464.42 mA W -1) and detectivity (D * ≈ 4.05 × 10 12 Jones). This work establishes stable UV photodetection via 3D perovskitoid compound, expanding the candidate materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
S stretch at ∼716 cm−1, determining LOD = 0.78 mM and LOQ = 2.60 mM. Time-resolved spectra capture the systematic decay of the 716 cm−1 band during the reaction, consistent with the disruption of the P4S10 cage and formation of thiophosphate intermediates. Early-stage kinetics are quantitatively described by the Finke–Watzky two-step model, and temperature-dependent rate constants yield Arrhenius and Eyring relationships with Ea(mw) = 39.59 kJ mol−1, ΔH‡ = 36.97 kJ mol−1, and ΔS‡ = −178.55 J mol−1 K−1. This combined in situ spectroscopic–kinetic approach offers a direct pathway to mechanistic understanding and parameter extraction in solution-based synthesis of sulfide SSEs.
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