Antonio García Alcaraz, Alicia Rey Planells, Arturo Espinosa Ferao, R. Streubel
Compared to aziridines, azaphosphiridines, which formally result from the replacement of a carbon atom by phosphorus, have been much less studied. In this work, accurate values for one of the most prominent properties, the ring strain energy (RSE), have been theoretically examined for a wide range of azaphosphiridine derivatives. Strongly related aspects of interest for developing the use of azaphosphiridines in heteroatom and polymer chemistry are ring opening reactions and polymerisations, the latter facilitated by their significantly high RSE. While methyl groups have little influence on the RSE, complexation with different metal moieties increases the RSE in all cases, and an increase was also found upon oxidation to the corresponding P-oxides and other σ5λ5-P derivatives. The highest RSE was found for the P-protonated azaphosphiridinium cation and azaphosphiridines with exocyclic double bonds. A correlation of the RSEs with the relaxed force constants of the endocyclic ring bonds and AIM-derived parameters in the ring critical points, such as the electron density, ρ(r), and the Lagrangian of the kinetic energy, G(r), was found. A relatively low barrier to P-C bond cleavage via nucleophilic attack of MeNH2 on phosphorus points to the possibility of ring-opening polymerisation
{"title":"A “phosphorus derivative” of aziridines: on the importance of ring strain energy and three heteropolar bonds in azaphosphiridines","authors":"Antonio García Alcaraz, Alicia Rey Planells, Arturo Espinosa Ferao, R. Streubel","doi":"10.1039/d4dt03117b","DOIUrl":"https://doi.org/10.1039/d4dt03117b","url":null,"abstract":"Compared to aziridines, azaphosphiridines, which formally result from the replacement of a carbon atom by phosphorus, have been much less studied. In this work, accurate values for one of the most prominent properties, the ring strain energy (RSE), have been theoretically examined for a wide range of azaphosphiridine derivatives. Strongly related aspects of interest for developing the use of azaphosphiridines in heteroatom and polymer chemistry are ring opening reactions and polymerisations, the latter facilitated by their significantly high RSE. While methyl groups have little influence on the RSE, complexation with different metal moieties increases the RSE in all cases, and an increase was also found upon oxidation to the corresponding P-oxides and other σ5<small><sup></sup></small>λ<small><sup>5</sup></small>-P derivatives. The highest RSE was found for the P-protonated azaphosphiridinium cation and azaphosphiridines with exocyclic double bonds. A correlation of the RSEs with the relaxed force constants of the endocyclic ring bonds and AIM-derived parameters in the ring critical points, such as the electron density, ρ(r), and the Lagrangian of the kinetic energy, G(r), was found. A relatively low barrier to P-C bond cleavage via nucleophilic attack of MeNH2<small><sub></sub></small> on phosphorus points to the possibility of ring-opening polymerisation","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"15 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935388","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}
Katarzyna Choroba, Joanna Palion-Gazda, Anna Kryczka, Ewa Malicka, Barbara Machura
Over the last five decades, diimine rhenium(I) tricarbonyl complexes have been extensively investigated due to their remarkable and widely tuned photophysical properties. These systems are regarded as attractive targets for design functional luminescent materials and performing fundamental studies of photoinduced processes in transition metal complexes. This review summarizes the latest developments concerning Re(I) tricarbonyl complexes bearing donor–acceptor (D–A) and donor–π–acceptor (D–π–A) ligands. Such compounds can be treated as bichromophoric systems with two close-lying excited states, metal-to-ligand charge transfer (MLCT) and intraligand-charge-transfer (ILCT). A role of ILCT transitions in controlling photobehaviour was discussed for Re(I) tricarbonyls with six different diimine cores decorated by various electron-rich amine, sulphur-based and π-conjugated aryl groups. It was evidenced that this approach is an effective tool for enhancement of the visible absorptivity, bathochromic emission shift and significant prolongation of the excited-state, opening up new possibilities in the development of more efficient materials and expand the range of their applications.
{"title":"Push-pull effect – how to effectively control photoinduced intramolecular charge transfer processes in rhenium(I) chromophores with ligands of D–A or D–π–A structure","authors":"Katarzyna Choroba, Joanna Palion-Gazda, Anna Kryczka, Ewa Malicka, Barbara Machura","doi":"10.1039/d4dt03237c","DOIUrl":"https://doi.org/10.1039/d4dt03237c","url":null,"abstract":"Over the last five decades, diimine rhenium(I) tricarbonyl complexes have been extensively investigated due to their remarkable and widely tuned photophysical properties. These systems are regarded as attractive targets for design functional luminescent materials and performing fundamental studies of photoinduced processes in transition metal complexes. This review summarizes the latest developments concerning Re(I) tricarbonyl complexes bearing donor–acceptor (D–A) and donor–π–acceptor (D–π–A) ligands. Such compounds can be treated as bichromophoric systems with two close-lying excited states, metal-to-ligand charge transfer (MLCT) and intraligand-charge-transfer (ILCT). A role of ILCT transitions in controlling photobehaviour was discussed for Re(I) tricarbonyls with six different diimine cores decorated by various electron-rich amine, sulphur-based and π-conjugated aryl groups. It was evidenced that this approach is an effective tool for enhancement of the visible absorptivity, bathochromic emission shift and significant prolongation of the excited-state, opening up new possibilities in the development of more efficient materials and expand the range of their applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"35 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935393","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}
Duyong Chen, Cheng Yi, Xin-Feng Li, Ren-He Zhou, Liyan Zhang, Rui Cai, Yin-Shan Meng, Tao Liu
Molecular materials that exhibit synergistic coupling between luminescence and spin-crossover (SCO) behaviors hold significant promise for applications in molecular sensors and memory devices. However, the rational design and underlying coupling mechanisms remain substantial challenges in this field. In this study, we utilize a luminescent complementary ligand pair as an intramolecular luminophore to construct a new Fe-based SCO complex, namely [FeL1L2](BF4)2·H2O (1-Fe, L1 is a 2,2′:6′,2″-terpyridine (TPY) derivative ligand, L2 is 2,6-Di-1H-pyrazol-1-yl-4-pyridinecarboxylic acid), and two isomorphic analogs (2-Co, [CoL1L2](BF4)2·H2O and 3-Zn, [ZnL1L2](BF4)2·H2O). Magnetic studies reveal that 1-Fe exhibits thermally induced SCO within the temperature range of 150 to 350 K. Variable-temperature fluorescence emission spectra analysis of the three complexes confirmed the occurrence of SCO-luminescence coupling in 1-Fe. Furthermore, variable-temperature UV-vis absorption spectra and time-dependent density functional theory (TD-DFT) calculations elucidate the intramolecular luminescent emission behavior, highlighting the critical role of charge transfer processes between the L1 ligand and FeII ions with different spin states. Our research presents a novel construction strategy for synthesizing synergistic SCO-luminescent materials and contributes to the understanding of the mechanisms underlying SCO-luminescence coupling.
{"title":"A Mononuclear Iron (II) Complex Constructed by Complementary Ligand Pair Exhibits Intrinsic Luminescence-Spin Crossover Coupling","authors":"Duyong Chen, Cheng Yi, Xin-Feng Li, Ren-He Zhou, Liyan Zhang, Rui Cai, Yin-Shan Meng, Tao Liu","doi":"10.1039/d4dt03177f","DOIUrl":"https://doi.org/10.1039/d4dt03177f","url":null,"abstract":"Molecular materials that exhibit synergistic coupling between luminescence and spin-crossover (SCO) behaviors hold significant promise for applications in molecular sensors and memory devices. However, the rational design and underlying coupling mechanisms remain substantial challenges in this field. In this study, we utilize a luminescent complementary ligand pair as an intramolecular luminophore to construct a new Fe-based SCO complex, namely [FeL<small><sub>1</sub></small>L<small><sub>2</sub></small>](BF<small><sub>4</sub></small>)<small><sub>2</sub></small>·H<small><sub>2</sub></small>O (<strong>1-Fe</strong>, L<small><sub>1</sub></small> is a 2,2′:6′,2″-terpyridine (TPY) derivative ligand, L<small><sub>2</sub></small> is 2,6-Di-1H-pyrazol-1-yl-4-pyridinecarboxylic acid), and two isomorphic analogs (<strong>2-Co</strong>, [CoL<small><sub>1</sub></small>L<small><sub>2</sub></small>](BF<small><sub>4</sub></small>)<small><sub>2</sub></small>·H<small><sub>2</sub></small>O and <strong>3-Zn</strong>, [ZnL<small><sub>1</sub></small>L<small><sub>2</sub></small>](BF<small><sub>4</sub></small>)<small><sub>2</sub></small>·H<small><sub>2</sub></small>O). Magnetic studies reveal that <strong>1-Fe</strong> exhibits thermally induced SCO within the temperature range of 150 to 350 K. Variable-temperature fluorescence emission spectra analysis of the three complexes confirmed the occurrence of SCO-luminescence coupling in <strong>1-Fe</strong>. Furthermore, variable-temperature UV-vis absorption spectra and time-dependent density functional theory (TD-DFT) calculations elucidate the intramolecular luminescent emission behavior, highlighting the critical role of charge transfer processes between the L<small><sub>1</sub></small> ligand and Fe<small><sup>II</sup></small> ions with different spin states. Our research presents a novel construction strategy for synthesizing synergistic SCO-luminescent materials and contributes to the understanding of the mechanisms underlying SCO-luminescence coupling.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"96 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929441","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}
The electrochemical proton reactivity of transition metal complexes receives intensive attention in the catalyst research. Proton-coupled electron transfer (PCET) process, influenced by coordination geometry, determines the catalytic reaction mechanisms. Additionally, the pKa of a proton source, as an external factor, plays a crucial role in regulating the proton transfer step. Understanding the effects of variations in the pKa of Brønsted acids on the PCET process is therefore essential. This study compares the PCET pathways of two high-spin cobalt (Co) complexes with contrasting exchange coupling interactions under acidic conditions with high and low pKa values. These findings reveal how proton reduction reactions in high-spin Co complexes are affected by internal factor of spin state, as well as external factor related to the proton source. The corresponding reaction mechanisms are also proposed based on these observations.
{"title":"Exploring Acidity-Dependent PCET Pathways in Imino-Bipyridyl Cobalt Complexes","authors":"Jueun Lee, Daeun Jung, Junhyeok Seo","doi":"10.1039/d4dt03221g","DOIUrl":"https://doi.org/10.1039/d4dt03221g","url":null,"abstract":"The electrochemical proton reactivity of transition metal complexes receives intensive attention in the catalyst research. Proton-coupled electron transfer (PCET) process, influenced by coordination geometry, determines the catalytic reaction mechanisms. Additionally, the pKa of a proton source, as an external factor, plays a crucial role in regulating the proton transfer step. Understanding the effects of variations in the pKa of Brønsted acids on the PCET process is therefore essential. This study compares the PCET pathways of two high-spin cobalt (Co) complexes with contrasting exchange coupling interactions under acidic conditions with high and low pKa values. These findings reveal how proton reduction reactions in high-spin Co complexes are affected by internal factor of spin state, as well as external factor related to the proton source. The corresponding reaction mechanisms are also proposed based on these observations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929444","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}
(Eu3+4[PTC]4–3)0.78(Eu3+[TREN-1,2-HOPO]3-)0.22 inorganic-organic hybrid nanoparticles (IOH-NPs) contain Eu3+, tris[(1-hydroxy-2-oxo-1,2-dihydropyridine-6-carboxamido)ethyl]amine (TREN-1,2-HOPO) and perylene-3,4,9,10-tetracarboxylate (PTC). The IOH-NPs are prepared in water and exhibit a rod-type shape, with a length of 60 nm and a diameter of 5 nm. Particle size and chemical composition are examined by different methods (SEM, DLS, FT-IR, TG, C/H/N analysis). With TREN-1,2-HOPO as antenna, the IOH-NPs show Eu3+-based red emission, whereas the PTC emission is totally quenched due to -stacking in the solid nanoparticles. After addition of carbonate, PTC is released from the IOH-NPs into solution, resulting in an increasing green emission of free PTC. The resulting carbonate-driven shift of the emission colour from red to green surprisingly allows to determine the carbonate concentration qualitatively and quantitatively in a concentration range of 1 µM to 2 mM and was tested for tap water as a specific example.
{"title":"Inorganic-Organic Hybrid Nanoparticles with Carbonate-triggered Emission-Colour-Shift","authors":"Christian Ritschel, Lena Daumann, Claus Feldmann","doi":"10.1039/d4dt02344g","DOIUrl":"https://doi.org/10.1039/d4dt02344g","url":null,"abstract":"(Eu3+4[PTC]4–3)0.78(Eu3+[TREN-1,2-HOPO]3-)0.22 inorganic-organic hybrid nanoparticles (IOH-NPs) contain Eu3+, tris[(1-hydroxy-2-oxo-1,2-dihydropyridine-6-carboxamido)ethyl]amine (TREN-1,2-HOPO) and perylene-3,4,9,10-tetracarboxylate (PTC). The IOH-NPs are prepared in water and exhibit a rod-type shape, with a length of 60 nm and a diameter of 5 nm. Particle size and chemical composition are examined by different methods (SEM, DLS, FT-IR, TG, C/H/N analysis). With TREN-1,2-HOPO as antenna, the IOH-NPs show Eu3+-based red emission, whereas the PTC emission is totally quenched due to -stacking in the solid nanoparticles. After addition of carbonate, PTC is released from the IOH-NPs into solution, resulting in an increasing green emission of free PTC. The resulting carbonate-driven shift of the emission colour from red to green surprisingly allows to determine the carbonate concentration qualitatively and quantitatively in a concentration range of 1 µM to 2 mM and was tested for tap water as a specific example.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"38 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929432","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}
Boyu Pan, Yao Wang, Bing Xu, Kangkang Wang, Liang Zhang, Zhixian He, Shengnan Zhang
Exploring new photoexcited phosphors has attracted attention for improving the performance of white LEDs. Here, an NaBa4Al2B8O18Cl3:xEu2+ phosphor with high color purity (94.11%) has been synthesized. The NBAC:0.035Eu2+ phosphor exhibits excellent color stability when the temperature increases from 298 K to 473 K. Impressively, the NBAC:0.035Eu2+ blue phosphor still exhibits excellent chemical stability after being immersed in water for 25 days. In addition, Eu2+ ions preferentially occupy the Na/Ba sites of the host structure, which contributes to the superior photoluminescence performance. Furthermore, near-ultraviolet (n-UV) pumped phosphor-converted white light-emitting diodes (pc-WLEDs) have been fabricated using the NBAC:0.035Eu2+ blue phosphor, green commercial phosphor (Sr,Ba)2SiO4:Eu2+ and red commercial phosphor (Ca,Sr)AlSiN3:Eu2+. The resulting device shows uniformly distributed warm white light with a color-rendering index (Ra) of 89.2 and a low correlated color temperature (CCT) of 4153 K. A series of excellent characteristics of NBAC:0.035Eu2+, including high-performance optical characteristics, a simple synthesis process and low economic cost, support its great application potential for use in warm white LED lighting systems.
{"title":"A narrow band blue phosphor NaBa4Al2B8O18Cl3:Eu2+ for white light emitting diodes","authors":"Boyu Pan, Yao Wang, Bing Xu, Kangkang Wang, Liang Zhang, Zhixian He, Shengnan Zhang","doi":"10.1039/d4dt02858a","DOIUrl":"https://doi.org/10.1039/d4dt02858a","url":null,"abstract":"Exploring new photoexcited phosphors has attracted attention for improving the performance of white LEDs. Here, an NaBa<small><sub>4</sub></small>Al<small><sub>2</sub></small>B<small><sub>8</sub></small>O<small><sub>18</sub></small>Cl<small><sub>3</sub></small>:<em>x</em>Eu<small><sup>2+</sup></small> phosphor with high color purity (94.11%) has been synthesized. The NBAC:0.035Eu<small><sup>2+</sup></small> phosphor exhibits excellent color stability when the temperature increases from 298 K to 473 K. Impressively, the NBAC:0.035Eu<small><sup>2+</sup></small> blue phosphor still exhibits excellent chemical stability after being immersed in water for 25 days. In addition, Eu<small><sup>2+</sup></small> ions preferentially occupy the Na/Ba sites of the host structure, which contributes to the superior photoluminescence performance. Furthermore, near-ultraviolet (n-UV) pumped phosphor-converted white light-emitting diodes (pc-WLEDs) have been fabricated using the NBAC:0.035Eu<small><sup>2+</sup></small> blue phosphor, green commercial phosphor (Sr,Ba)<small><sub>2</sub></small>SiO<small><sub>4</sub></small>:Eu<small><sup>2+</sup></small> and red commercial phosphor (Ca,Sr)AlSiN<small><sub>3</sub></small>:Eu<small><sup>2+</sup></small>. The resulting device shows uniformly distributed warm white light with a color-rendering index (<em>R</em><small><sub>a</sub></small>) of 89.2 and a low correlated color temperature (CCT) of 4153 K. A series of excellent characteristics of NBAC:0.035Eu<small><sup>2+</sup></small>, including high-performance optical characteristics, a simple synthesis process and low economic cost, support its great application potential for use in warm white LED lighting systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"73 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929433","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}
The present work reported a lucid and improved hydrothermal methodology for synthesis of MoSe2 nanoflowers (MNF) at 210 °C. To observe the effect of temperature on fascinating properties, the process temperature was modified by ±10 °C. The as-prepared MNF were found to consist of 2D nanosheets which assembled into 3D flower-like hierarchical morphology via Van-der Waals force. The elemental-composition and -mapping of MNF reveals that the constituents are uniformly distributed throughout the material. Crystallography and structural analyses confirmed that the as-synthesized MNF were of highly crystalline nature with two-layer hexagonal (2H) phase of MoSe2 (2H-MoSe2). Additionally, microstructure and lattice scale features of MNF studied using HRTEM disclosed that ultrathin nanosheets having thickness 3 nm, which were few atomic layers thick. A plausible formation and growth mechanism of as-prepared MNF was also proposed. For the purpose of developing supercapacitors, the electrochemical energy-storage characteristic of synthesized MNF was examined. Maximum specific capacitance of 284.8 F g-1 at 5 mV s-1 scan rate was demonstrated by the three-electrode setup, and capacitance retention was about 88% even after 10,000 cycles. As an electrode material for supercapacitors, MNF has great potential due to its high specific capacitance and exceptional cycle stability.
{"title":"Structural-Morphological Insights into Optimization of Hydrothermally Synthesized MoSe2 Nanoflowers for Improving Supercapacitor Application","authors":"Poonam Yadav, Rohit Yadav, Jitesh Pani, Ram Meher Singh, Davender Singh, Kumari Kusum, Hitesh Borkar, Jitendra Gangwar","doi":"10.1039/d4dt02993c","DOIUrl":"https://doi.org/10.1039/d4dt02993c","url":null,"abstract":"The present work reported a lucid and improved hydrothermal methodology for synthesis of MoSe2 nanoflowers (MNF) at 210 °C. To observe the effect of temperature on fascinating properties, the process temperature was modified by ±10 °C. The as-prepared MNF were found to consist of 2D nanosheets which assembled into 3D flower-like hierarchical morphology via Van-der Waals force. The elemental-composition and -mapping of MNF reveals that the constituents are uniformly distributed throughout the material. Crystallography and structural analyses confirmed that the as-synthesized MNF were of highly crystalline nature with two-layer hexagonal (2H) phase of MoSe2 (2H-MoSe2). Additionally, microstructure and lattice scale features of MNF studied using HRTEM disclosed that ultrathin nanosheets having thickness 3 nm, which were few atomic layers thick. A plausible formation and growth mechanism of as-prepared MNF was also proposed. For the purpose of developing supercapacitors, the electrochemical energy-storage characteristic of synthesized MNF was examined. Maximum specific capacitance of 284.8 F g-1 at 5 mV s-1 scan rate was demonstrated by the three-electrode setup, and capacitance retention was about 88% even after 10,000 cycles. As an electrode material for supercapacitors, MNF has great potential due to its high specific capacitance and exceptional cycle stability.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"82 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929437","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}
Hong Shang, jia peng, Yougui Zhou, Lihua Guo, Huipeng Li, Weiliang Wang
Graphdiyne (GDY), which is composed of benzene rings and acetylene linkages units, is a new allotrope of carbon material. Especially, the large triangular pores, with a diameter of 5.4 Å, theoretically predict a higher lithium embedding density compared to traditional graphite anodes, enabling GDY to serve as an effective energy storage material in lithium−ion (Li−ion) battery. GDY is primarily synthesized through the cross−coupling reaction of hexaethynylbenzene (HEB). Under similar preparation conditions, the cross−coupling reaction of other aryne precursors, instead of HEB, results in many GDY heteroatom−doped derivatives. This introduces plenty of heteroatomic defects as well as electrochemically active sites, potentially enhancing electrochemical performance. Recent advancements have been made in utilizing GDY and its heteroatom−doped derivatives as electrode materials or composite materials in Li−ion/metal batteries. This review systematically summarizes the strategies developed for GDY and its heteroatom−doped derivatives. Notably, recent research on the effects of morphology and chemical/electronic structure on performance, particularly new conceptual mechanisms in Li−ion/metal batteries including self−expanding Li−ion transport channels and capture/pores filling−intercalation hybrid mechanism, is briefly described. The results presented here highlight the significant potential of GDY and its heteroatom−doped derivatives for energy storage applications and inspire interest in further development.
{"title":"Graphdiyne and its heteroatom−doped derivatives for Li−ion/metal batteries","authors":"Hong Shang, jia peng, Yougui Zhou, Lihua Guo, Huipeng Li, Weiliang Wang","doi":"10.1039/d4dt03268c","DOIUrl":"https://doi.org/10.1039/d4dt03268c","url":null,"abstract":"Graphdiyne (GDY), which is composed of benzene rings and acetylene linkages units, is a new allotrope of carbon material. Especially, the large triangular pores, with a diameter of 5.4 Å, theoretically predict a higher lithium embedding density compared to traditional graphite anodes, enabling GDY to serve as an effective energy storage material in lithium−ion (Li−ion) battery. GDY is primarily synthesized through the cross−coupling reaction of hexaethynylbenzene (HEB). Under similar preparation conditions, the cross−coupling reaction of other aryne precursors, instead of HEB, results in many GDY heteroatom−doped derivatives. This introduces plenty of heteroatomic defects as well as electrochemically active sites, potentially enhancing electrochemical performance. Recent advancements have been made in utilizing GDY and its heteroatom−doped derivatives as electrode materials or composite materials in Li−ion/metal batteries. This review systematically summarizes the strategies developed for GDY and its heteroatom−doped derivatives. Notably, recent research on the effects of morphology and chemical/electronic structure on performance, particularly new conceptual mechanisms in Li−ion/metal batteries including self−expanding Li−ion transport channels and capture/pores filling−intercalation hybrid mechanism, is briefly described. The results presented here highlight the significant potential of GDY and its heteroatom−doped derivatives for energy storage applications and inspire interest in further development.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"117 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929434","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}
Partha Mahata, Mohabul Alam Mondal, Chhatan Das, Arunava Misra
This study presents the synthesis of a Cd(II) based hydrophobic three dimensional crystalline network material (CNM), [Cd3(L)2(LH)2(bpe)2], {L= {4,4'-(hexafluroisopropylidine)bis(benzoate)} and 1,2-di(4-pyridyl) ethylene (bpe)}, 1(Cd), by employing the slow-diffusion method. The three-dimensional structure of 1(Cd) was determined by single crystal X-ray diffraction and characterized by powder X-ray diffraction (PXRD), FT-IR spectroscopy and thermogravimetric analysis (TGA). Subsequent, post-synthetic modification of 1(Cd) with Cu(II) at room temperature led to the formation of isostructural 1(Cu) with partial substitution. This transformation, unattainable through de-novo synthesis, was monitored using energy dispersive X-ray analysis (EDX), PXRD, FT-IR spectroscopy, and through visual observation confirming a single crystal to single crystal metal exchange. The modified material, 1(Cu), exhibited red-shifted emission with enhanced thermal stability and tenfold increase in N2 uptake. Furthermore, the catalytic potential of 1(Cd) in aza-Michael addition reactions of α, β-unsaturated olefins to nucleophilic aromatic/aliphatic amines was demonstrated successfully under ambient conditions. This approach employed a heterogeneous and acid-base free methodology showcasing the versatility and effectiveness of 1(Cd) as a catalyst.
{"title":"Cd-Based Crystalline Network Material: Catalytic Properties and Post Synthetic Metal-Ion Metathesis with Enhanced Stability and Gas Sorption Behaviour","authors":"Partha Mahata, Mohabul Alam Mondal, Chhatan Das, Arunava Misra","doi":"10.1039/d4dt03287j","DOIUrl":"https://doi.org/10.1039/d4dt03287j","url":null,"abstract":"This study presents the synthesis of a Cd(II) based hydrophobic three dimensional crystalline network material (CNM), [Cd3(L)2(LH)2(bpe)2], {L= {4,4'-(hexafluroisopropylidine)bis(benzoate)} and 1,2-di(4-pyridyl) ethylene (bpe)}, 1(Cd), by employing the slow-diffusion method. The three-dimensional structure of 1(Cd) was determined by single crystal X-ray diffraction and characterized by powder X-ray diffraction (PXRD), FT-IR spectroscopy and thermogravimetric analysis (TGA). Subsequent, post-synthetic modification of 1(Cd) with Cu(II) at room temperature led to the formation of isostructural 1(Cu) with partial substitution. This transformation, unattainable through de-novo synthesis, was monitored using energy dispersive X-ray analysis (EDX), PXRD, FT-IR spectroscopy, and through visual observation confirming a single crystal to single crystal metal exchange. The modified material, 1(Cu), exhibited red-shifted emission with enhanced thermal stability and tenfold increase in N2 uptake. Furthermore, the catalytic potential of 1(Cd) in aza-Michael addition reactions of α, β-unsaturated olefins to nucleophilic aromatic/aliphatic amines was demonstrated successfully under ambient conditions. This approach employed a heterogeneous and acid-base free methodology showcasing the versatility and effectiveness of 1(Cd) as a catalyst.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"36 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929435","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}
Suying Li, Yan Chen, Shuaiqi Feng, Zhifang Liu, Lin-Ling Gan, Qing-Peng Wang
The Pt(IV) complexes as prodrugs of Pt(II) drugs exhibit numerous advantages such as enhanced stability, reduced toxicity, increased oral bioavailability, and efficacy in overcoming the drug resistance of Pt(II) compounds, which underscore their significant potential in the advancement of novel Pt anticancer agents. Furthermore, protective autophagy is pivotal in sustaining tumor cell homeostasis and modulating the tumor microenvironment (TME), thereby representing a critical target for the development of antitumor drugs. Specific inhibition or activation of autophagy during chemotherapy would break the internal homeostasis in TME, and increase antitumor activities. Consequently, developing novel Pt(IV) antitumor agents with autophagy-targeting capabilities by incorporating autophagy-regulating moieties into the Pt(IV) framework has emerged as a hot topic in the discovery of novel Pt drugs. Herein, the research progress in novel Pt(IV) antitumor drugs with autophagy-targeted properties are systematically reviewed based on the literature. The future challenges and perspectives of this fascinating class of conjugates were also discussed, aiming to provide new insights and approaches for the future design and investigation of novel Pt antitumor drugs.
{"title":"Autophagy-Targeted Platinum(IV) Agents: A New Horizon in Antitumor Drug Development","authors":"Suying Li, Yan Chen, Shuaiqi Feng, Zhifang Liu, Lin-Ling Gan, Qing-Peng Wang","doi":"10.1039/d4dt03162h","DOIUrl":"https://doi.org/10.1039/d4dt03162h","url":null,"abstract":"The Pt(IV) complexes as prodrugs of Pt(II) drugs exhibit numerous advantages such as enhanced stability, reduced toxicity, increased oral bioavailability, and efficacy in overcoming the drug resistance of Pt(II) compounds, which underscore their significant potential in the advancement of novel Pt anticancer agents. Furthermore, protective autophagy is pivotal in sustaining tumor cell homeostasis and modulating the tumor microenvironment (TME), thereby representing a critical target for the development of antitumor drugs. Specific inhibition or activation of autophagy during chemotherapy would break the internal homeostasis in TME, and increase antitumor activities. Consequently, developing novel Pt(IV) antitumor agents with autophagy-targeting capabilities by incorporating autophagy-regulating moieties into the Pt(IV) framework has emerged as a hot topic in the discovery of novel Pt drugs. Herein, the research progress in novel Pt(IV) antitumor drugs with autophagy-targeted properties are systematically reviewed based on the literature. The future challenges and perspectives of this fascinating class of conjugates were also discussed, aiming to provide new insights and approaches for the future design and investigation of novel Pt antitumor drugs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"14 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929439","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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