Some pincer type mono- and poly-nuclear Pd(II) and Pt(II) complexes bearing imidazo[1,5-a]pyridine and imidazolylpyridine moiety were synthesized and characterized by using several spectroscopic methods. Determination of molecular structures of all complexes by single crystal X-ray diffraction studies revealed a distorted square planar geometry around the bivalent palladium and platinum in all complexes. These Pd(II) complexes have been observed to display high catalytic activity in various reaction such as Suzuki-Miyaura cross-coupling reaction, transfer hydrogenation reaction, and alkyne homocoupling. The theoretical study was also well matched with experimental data of all catalysts. Substantial deviations in the catalytic activity were observed by changing the co-ligand, binding mode of the ligand and the number of metal centre. Under optimal conditions, Suzuki cross-coupling and the transfer hydrogenation reaction were accomplished proficiently with wide functional group possibility by taking only 0.1 mol% of tetranuclear Pd(II) complex (5) as catalyst. Intermediates in Suzuki coupling reaction were also detected by using mass spectroscopy. Among all studied complexes, the tetra nuclear palladium complex exhibited high catalytic activity. Further Pd(II) complexes were tested in a model reaction of homocoupling of phenylacetylene and produce diphenylbutadiyne in excellent yield. Also, interaction study of all the complexes with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) were investigated using electronic spectroscopy Absorption study showed minor groove binding of DNA with these complexes while intercalative binding was observed by all complexes through displacement of ethidium bromide (EB) in EB-DNA by quenching of fluorescence intensity. The complexes were also displayed high binding affinity toward BSA confirmed by emission, synchronous fluorescence, and steady state fluorescence anisotropy measurement. Moreover, the pharmacokinetic properties of two bioactive compounds (3s and 3t) obtained from Suzuki coupling reaction were calculated and to evaluate their activity as leukotriene A4 hydrolase (LTA4H) inhibitor, these molecules were docked with human LTA4H enzyme.
{"title":"Palladium(II) and Platinum(II) Complexes of Disubstituted Imidazo[1,5-a]Pyridine and Imidazolylpyridine: Coordination Chemistry, Versatile Catalysis, Biophysical Study","authors":"AMLAN RANJAN RAYASINGH, Vadivelu Manivannan","doi":"10.1039/d5dt00346f","DOIUrl":"https://doi.org/10.1039/d5dt00346f","url":null,"abstract":"Some pincer type mono- and poly-nuclear Pd(II) and Pt(II) complexes bearing imidazo[1,5-a]pyridine and imidazolylpyridine moiety were synthesized and characterized by using several spectroscopic methods. Determination of molecular structures of all complexes by single crystal X-ray diffraction studies revealed a distorted square planar geometry around the bivalent palladium and platinum in all complexes. These Pd(II) complexes have been observed to display high catalytic activity in various reaction such as Suzuki-Miyaura cross-coupling reaction, transfer hydrogenation reaction, and alkyne homocoupling. The theoretical study was also well matched with experimental data of all catalysts. Substantial deviations in the catalytic activity were observed by changing the co-ligand, binding mode of the ligand and the number of metal centre. Under optimal conditions, Suzuki cross-coupling and the transfer hydrogenation reaction were accomplished proficiently with wide functional group possibility by taking only 0.1 mol% of tetranuclear Pd(II) complex (5) as catalyst. Intermediates in Suzuki coupling reaction were also detected by using mass spectroscopy. Among all studied complexes, the tetra nuclear palladium complex exhibited high catalytic activity. Further Pd(II) complexes were tested in a model reaction of homocoupling of phenylacetylene and produce diphenylbutadiyne in excellent yield. Also, interaction study of all the complexes with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) were investigated using electronic spectroscopy Absorption study showed minor groove binding of DNA with these complexes while intercalative binding was observed by all complexes through displacement of ethidium bromide (EB) in EB-DNA by quenching of fluorescence intensity. The complexes were also displayed high binding affinity toward BSA confirmed by emission, synchronous fluorescence, and steady state fluorescence anisotropy measurement. Moreover, the pharmacokinetic properties of two bioactive compounds (3s and 3t) obtained from Suzuki coupling reaction were calculated and to evaluate their activity as leukotriene A4 hydrolase (LTA4H) inhibitor, these molecules were docked with human LTA4H enzyme.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"58 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776133","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 Stawicka, Maciej Trejda, Aleksandra Rybka, Maria Ziolek
Two different SBA-15 silicas with long and short channels, containing zirconium species, were prepared and used as supports for molybdenum additives. The resulting materials were characterized and tested as catalysts for extractive catalytic oxidative desulfurization (ECODS) of dibenzothiophene (DBT) using acetonitrile as a solvent and H2O2 as an oxidant. The synthesis procedure for the zirconium-containing silicas influenced both the zirconium loading and its distribution, i.e., whether it was incorporated into the framework or present in extra-framework positions. Additionally, the choice of support for molybdenum inclusion affected the amount of modifier loaded and its resistance to leaching, which collectively impacted the acidic and basic properties of the synthesized catalysts. The textural and surface properties of the materials were evaluated using low-temperature nitrogen adsorption/desorption, XRD, SEM-EDS, FT-IR-ATR, XPS, and UV-vis. The acidity and basicity of the samples were evaluated using FT-IR spectroscopy with pyridine adsorption/desorption and test reactions including 2-propanol dehydration/dehydrogenation and 2,5-hexanedione cyclization/dehydration. The catalytic activity was measured in ECODS. The Mo/ZrSBA-15-S catalyst demonstrated the best performance in DBT removal from the oil phase, achieving approximately 92% conversion of DBT within 120 minutes at 60 °C. This superior activity was attributed to the material's high acidity strength.
{"title":"Removal of dibenzothiophene by extraction and catalytic oxidation using long- and short-channel SBA-15 containing Zr and Mo species","authors":"Katarzyna Stawicka, Maciej Trejda, Aleksandra Rybka, Maria Ziolek","doi":"10.1039/d5dt00043b","DOIUrl":"https://doi.org/10.1039/d5dt00043b","url":null,"abstract":"Two different SBA-15 silicas with long and short channels, containing zirconium species, were prepared and used as supports for molybdenum additives. The resulting materials were characterized and tested as catalysts for extractive catalytic oxidative desulfurization (ECODS) of dibenzothiophene (DBT) using acetonitrile as a solvent and H<small><sub>2</sub></small>O<small><sub>2</sub></small> as an oxidant. The synthesis procedure for the zirconium-containing silicas influenced both the zirconium loading and its distribution, <em>i.e.</em>, whether it was incorporated into the framework or present in extra-framework positions. Additionally, the choice of support for molybdenum inclusion affected the amount of modifier loaded and its resistance to leaching, which collectively impacted the acidic and basic properties of the synthesized catalysts. The textural and surface properties of the materials were evaluated using low-temperature nitrogen adsorption/desorption, XRD, SEM-EDS, FT-IR-ATR, XPS, and UV-vis. The acidity and basicity of the samples were evaluated using FT-IR spectroscopy with pyridine adsorption/desorption and test reactions including 2-propanol dehydration/dehydrogenation and 2,5-hexanedione cyclization/dehydration. The catalytic activity was measured in ECODS. The Mo/ZrSBA-15-S catalyst demonstrated the best performance in DBT removal from the oil phase, achieving approximately 92% conversion of DBT within 120 minutes at 60 °C. This superior activity was attributed to the material's high acidity strength.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"197 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766572","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}
Muhammad Zada, Qiuyue Zhang, Qaiser Mahmood, Yanping Ma, Yang Sun, Wen Hua Sun
The suboptimal catalytic performance of bis(arylimino)pyridyliron precatalysts in ethylene polymerization at elevated temperatures remains a significant challenge. In this study, a series of six bis(arylimino)pyridyliron chloride precatalysts with incorporation of benzosuberyl steric bulk was prepared and investigated for ethylene polymerization. Capping the axial sites of the iron center with benzosuberyl steric bulk resulted in π−π interactions between the phenyl group and the chelate backbone, with a distance of ca. 3.293 Å for Fe3iPr, shorter than the sum of the van der Waals radii of carbon atoms (3.4 Å), as confirmed by single-crystal X-ray diffraction. These non-covalent interactions enhanced the thermal stability, catalytic activity, and polymer molecular weights. On activation with MAO or MMAO cocatalysts, these precatalysts exhibited the maximum activity of 2.53 × 107 g mol-1 h-1 at 80 oC and 1.88 × 107 g mol-1 h-1 at 100 oC, demonstrating their unprecedented thermal stability. The molecular weight of the produced polyethylene remained high, even at elevated temperatures. Moreover, ligand modifications had a pronounced impact on polymerization outcomes: the least sterically hindered complex, while producing comparatively lower molecular weight polyethylene, displayed higher activity and the most sterically hindered one showed opposite tendency. The molecular weight dispersity of polyethylene showed a strong correlation with the precatalyst structure and reaction conditions. High melting points confirmed the presence of strictly linear structures with high vinyl end groups (up to 74%), as verified by 1H/13C NMR spectra. A comparison of structurally related iron precatalysts emphasized significant improvements in both thermal stability and catalytic activity, attributed to the π−π interactions present in the current iron precatalysts.
{"title":"π−π Interactions Strategy for Targeting Highly Thermostable Bis(arylimino)pyridyliron Precatalysts in Ethylene Polymerization","authors":"Muhammad Zada, Qiuyue Zhang, Qaiser Mahmood, Yanping Ma, Yang Sun, Wen Hua Sun","doi":"10.1039/d5dt00571j","DOIUrl":"https://doi.org/10.1039/d5dt00571j","url":null,"abstract":"The suboptimal catalytic performance of bis(arylimino)pyridyliron precatalysts in ethylene polymerization at elevated temperatures remains a significant challenge. In this study, a series of six bis(arylimino)pyridyliron chloride precatalysts with incorporation of benzosuberyl steric bulk was prepared and investigated for ethylene polymerization. Capping the axial sites of the iron center with benzosuberyl steric bulk resulted in π−π interactions between the phenyl group and the chelate backbone, with a distance of ca. 3.293 Å for Fe3iPr, shorter than the sum of the van der Waals radii of carbon atoms (3.4 Å), as confirmed by single-crystal X-ray diffraction. These non-covalent interactions enhanced the thermal stability, catalytic activity, and polymer molecular weights. On activation with MAO or MMAO cocatalysts, these precatalysts exhibited the maximum activity of 2.53 × 10<small><sup>7</sup></small> g mol<small><sup>-1</sup></small> h<small><sup>-1</sup></small> at 80 <small><sup>o</sup></small>C and 1.88 × 10<small><sup>7</sup></small> g mol<small><sup>-1</sup></small> h<small><sup>-1</sup></small> at 100 <small><sup>o</sup></small>C, demonstrating their unprecedented thermal stability. The molecular weight of the produced polyethylene remained high, even at elevated temperatures. Moreover, ligand modifications had a pronounced impact on polymerization outcomes: the least sterically hindered complex, while producing comparatively lower molecular weight polyethylene, displayed higher activity and the most sterically hindered one showed opposite tendency. The molecular weight dispersity of polyethylene showed a strong correlation with the precatalyst structure and reaction conditions. High melting points confirmed the presence of strictly linear structures with high vinyl end groups (up to 74%), as verified by <small><sup>1</sup></small>H/<small><sup>13</sup></small>C NMR spectra. A comparison of structurally related iron precatalysts emphasized significant improvements in both thermal stability and catalytic activity, attributed to the π−π interactions present in the current iron precatalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767019","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}
Hyolim Jung, Hae LIn Yang, Gi-Beom Park, Ji-Min Kim, Jin-Seong Park
This study investigated the synthesis of sp2 carbons using molecular layer deposition (MLD) with tincone, which utilized tetrakis(dimethylamido)tin (TDMASn) as the metal precursor and 4-mercaptophenol (4MP) as the organic linker. Tincone films were deposited at 100 °C without impurities and then subjected to vacuum post-annealing in a tube furnace to induce graphitization. Compositional and structural analyses revealed significant changes as the annealing temperature increased, including the breakdown of the bonds between Sn, O, S, and C . This process led to the reduction of Sn, O, and S and the formation of sp2 carbons. At 400 °C, the film thickness was reduced by 57.5%, and the refractive index increased from 1.8 to 1.97, as confirmed by the emergence of G-band and 2D-band peaks in the Raman spectra. X-ray photoelectron spectroscopy analysis indicated that the residual Sn content decreased to 0.75% at 600 °C. Interestingly, at temperatures above 400 °C, unique behavior was observed: increased C-S bonding disrupted the graphite structure due to the thiol (-SH) groups in 4MP. This disruption led to a reduction in C-C bonding and a decrease in the G-band peak in the Raman spectra. This study provides the first detailed investigation of the role of S in the graphitization of tincone, highlighting its impact on sp2 carbon formation and emphasizing the importance of the careful selection of precursors and linkers in MLD processes.
本研究利用分子层沉积（MLD）技术，以四（二甲基氨基）锡（TDMASn）为金属前驱体，4-巯基苯酚（4MP）为有机连接剂，研究了sp2 碳的合成。Tincone 薄膜在不含杂质的 100 °C 下沉积，然后在管式炉中进行真空后退火以诱导石墨化。成分和结构分析表明，随着退火温度的升高，锡、O、S 和 C 之间的键发生了显著变化。这一过程导致了 Sn、O 和 S 的减少以及 sp2 碳的形成。在 400 °C 时，薄膜厚度减少了 57.5%，折射率从 1.8 增加到 1.97，拉曼光谱中出现的 G 波段和 2D 波段峰证实了这一点。X 射线光电子能谱分析表明，在 600 °C 时，残余锡含量降至 0.75%。有趣的是，在温度高于 400 °C 时，观察到了独特的行为：由于 4MP 中的硫醇（-SH）基团，C-S 键的增加破坏了石墨结构。这种破坏导致 C-C 键的减少和拉曼光谱中 G 波段峰的降低。本研究首次详细探讨了 S 在锑酮石墨化过程中的作用，强调了其对 sp2 碳形成的影响，并强调了在 MLD 过程中仔细选择前体和连接体的重要性。
{"title":"Graphitization of Tincone via Molecular Layer Deposition: Investigating Sulfur’s Role and Structural Impacts","authors":"Hyolim Jung, Hae LIn Yang, Gi-Beom Park, Ji-Min Kim, Jin-Seong Park","doi":"10.1039/d5dt00529a","DOIUrl":"https://doi.org/10.1039/d5dt00529a","url":null,"abstract":"This study investigated the synthesis of sp2 carbons using molecular layer deposition (MLD) with tincone, which utilized tetrakis(dimethylamido)tin (TDMASn) as the metal precursor and 4-mercaptophenol (4MP) as the organic linker. Tincone films were deposited at 100 °C without impurities and then subjected to vacuum post-annealing in a tube furnace to induce graphitization. Compositional and structural analyses revealed significant changes as the annealing temperature increased, including the breakdown of the bonds between Sn, O, S, and C . This process led to the reduction of Sn, O, and S and the formation of sp2 carbons. At 400 °C, the film thickness was reduced by 57.5%, and the refractive index increased from 1.8 to 1.97, as confirmed by the emergence of G-band and 2D-band peaks in the Raman spectra. X-ray photoelectron spectroscopy analysis indicated that the residual Sn content decreased to 0.75% at 600 °C. Interestingly, at temperatures above 400 °C, unique behavior was observed: increased C-S bonding disrupted the graphite structure due to the thiol (-SH) groups in 4MP. This disruption led to a reduction in C-C bonding and a decrease in the G-band peak in the Raman spectra. This study provides the first detailed investigation of the role of S in the graphitization of tincone, highlighting its impact on sp2 carbon formation and emphasizing the importance of the careful selection of precursors and linkers in MLD processes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776180","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}
Searching for novel organic-inorganic hybrid perovskite materials with long-term stability and excellent optoelectronic properties is the focus of optoelectronic field. High-pressure as a special thermodynamic parameter, offers a promising avenue for discovering and designing materials with optimized performance. However, the data-driven pressure-engineered structure-property relationships remains scarce, leading to an insufficiently understanding of the physical rules by which pressure regulation influences the microstructure and electronic properties of materials. In this study, we conduct high-throughput first-principles calculation to construct a database of hundreds of cubic ABX3 candidates and evaluate their property evolutions under pressures ranging from 0 to 10 GPa. Through systematic assessments of the crystallographic stability, thermodynamic stability, and electronic properties, we obtain the following findings: the B-site metal predominantly determines crystal structure stability; the X-site halogen governs thermodynamic stability; and the ionic radius of A-site organic cation plays a pivotal role in modulating the electronic properties. Based on extensive theoretical calculations, this study confirms the influence of “single-component” effect, further enriching the existing knowledge that the synergistic changes in bond length or bond angle between B-site and X-site under pressure are the main factors affecting material properties. The insights derived from current analysis provide a valuable foundation for rational design of the optimized OIHP materials under pressure.
{"title":"Insight into the pressure-engineered structure-property relationship of organic-inorganic hybrid perovskites through high-throughput first-principles calculations","authors":"Ling-Jun He, Huan-Huan Yang, Wen-Yong Lai","doi":"10.1039/d5dt00365b","DOIUrl":"https://doi.org/10.1039/d5dt00365b","url":null,"abstract":"Searching for novel organic-inorganic hybrid perovskite materials with long-term stability and excellent optoelectronic properties is the focus of optoelectronic field. High-pressure as a special thermodynamic parameter, offers a promising avenue for discovering and designing materials with optimized performance. However, the data-driven pressure-engineered structure-property relationships remains scarce, leading to an insufficiently understanding of the physical rules by which pressure regulation influences the microstructure and electronic properties of materials. In this study, we conduct high-throughput first-principles calculation to construct a database of hundreds of cubic ABX3 candidates and evaluate their property evolutions under pressures ranging from 0 to 10 GPa. Through systematic assessments of the crystallographic stability, thermodynamic stability, and electronic properties, we obtain the following findings: the B-site metal predominantly determines crystal structure stability; the X-site halogen governs thermodynamic stability; and the ionic radius of A-site organic cation plays a pivotal role in modulating the electronic properties. Based on extensive theoretical calculations, this study confirms the influence of “single-component” effect, further enriching the existing knowledge that the synergistic changes in bond length or bond angle between B-site and X-site under pressure are the main factors affecting material properties. The insights derived from current analysis provide a valuable foundation for rational design of the optimized OIHP materials under pressure.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"16 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776135","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}
Phenol is an important intermediate for high value chemicals. Current phenol production via a three-step cumene process causes severe energy-waste and environmental problems. The conversion of benzene to phenol under mild condition can be achieved by oxidation with Cu-based zeolites. However, conventional microporous zeolite suffers from severe diffusion limitation, especially when bulky molecules are involved, such as benzene. In this work, we used a hierarchically macro-meso-microporous ZSM-5 single crystal (Hier-ZSM-5) as substrate for Cu species (Cu@Hier-ZSM-5). Irregular morphology of opal-like Hier-ZSM-5 exhibits abundant surface Si-OH groups and provides a platform for stabilizing Cu2+ sites. Meanwhile, hierarchical porosity provides significantly improved diffusion ability of bulky molecules. As a result, excellent selective oxidation performance of benzene was obtained with the Cu@Hier-ZSM-5, achieving a conversion of 77% and a phenol selectivity of 73%, which is 1.5 times and 2 times of these obtained with a catalyst based on a microporous ZSM-5, respectively. Species of CuOOH were identified as an important intermediate for benzene oxidation. This hierarchical zeolite system with a synergistic effect of site anchoring and molecular diffusion presents an excellent platform for catalyst design.
{"title":"Anchoring Cu sites in a hierarchical single-crystalline ZSM-5 zeolite for enhanced diffusion and benzene oxidation","authors":"Xue-Qing Xu, Shen Yu, Xing-Yu Yue, Zhan Liu, Jia-Min Lyu, Yi-Long Wang, Zhi-Yi Hu, Yu Li, Li-Hua Chen, Bao-Lian Su","doi":"10.1039/d5dt00442j","DOIUrl":"https://doi.org/10.1039/d5dt00442j","url":null,"abstract":"Phenol is an important intermediate for high value chemicals. Current phenol production via a three-step cumene process causes severe energy-waste and environmental problems. The conversion of benzene to phenol under mild condition can be achieved by oxidation with Cu-based zeolites. However, conventional microporous zeolite suffers from severe diffusion limitation, especially when bulky molecules are involved, such as benzene. In this work, we used a hierarchically macro-meso-microporous ZSM-5 single crystal (Hier-ZSM-5) as substrate for Cu species (Cu@Hier-ZSM-5). Irregular morphology of opal-like Hier-ZSM-5 exhibits abundant surface Si-OH groups and provides a platform for stabilizing Cu2+ sites. Meanwhile, hierarchical porosity provides significantly improved diffusion ability of bulky molecules. As a result, excellent selective oxidation performance of benzene was obtained with the Cu@Hier-ZSM-5, achieving a conversion of 77% and a phenol selectivity of 73%, which is 1.5 times and 2 times of these obtained with a catalyst based on a microporous ZSM-5, respectively. Species of CuOOH were identified as an important intermediate for benzene oxidation. This hierarchical zeolite system with a synergistic effect of site anchoring and molecular diffusion presents an excellent platform for catalyst design.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"61 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776181","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}
Wenfeng Liu, Jicheng Zhou, Hua Yang, Zhiyong Chen, Zao Yi
This study presents a high-efficiency solar cell featuring dual hole transport layers (HTL) and dual electron transport layers (ETL), with a structure of ITO/ZnO/CDS/CH3NH3PbI3/Se-Te: Cu2O/NiO/Al. The combination of ZnO/CDS as dual ETL and Se-Te: Cu2O/NiO as dual HTL optimizes carrier transport and collection efficiency. Simulations based on the Poisson equation and carrier continuity equations demonstrate that this design significantly reduces interfacial recombination losses and improves band alignment. As a result, the cell achieves a fill factor (FF) of 84.04 %, a short-circuit current density (Jsc) of 21.39 mA/cm², and a power conversion efficiency (PCE) of 20.14 %. The research highlights the critical role of the dual transport layer structure in enhancing carrier separation and transport efficiency, providing valuable theoretical and experimental insights for the design and optimization of future high-performance solar cells.
{"title":"Optimizing energy levels in perovskite solar cells with dual hole and dual electron transport layers","authors":"Wenfeng Liu, Jicheng Zhou, Hua Yang, Zhiyong Chen, Zao Yi","doi":"10.1039/d5dt00463b","DOIUrl":"https://doi.org/10.1039/d5dt00463b","url":null,"abstract":"This study presents a high-efficiency solar cell featuring dual hole transport layers (HTL) and dual electron transport layers (ETL), with a structure of ITO/ZnO/CDS/CH3NH3PbI3/Se-Te: Cu2O/NiO/Al. The combination of ZnO/CDS as dual ETL and Se-Te: Cu2O/NiO as dual HTL optimizes carrier transport and collection efficiency. Simulations based on the Poisson equation and carrier continuity equations demonstrate that this design significantly reduces interfacial recombination losses and improves band alignment. As a result, the cell achieves a fill factor (FF) of 84.04 %, a short-circuit current density (Jsc) of 21.39 mA/cm², and a power conversion efficiency (PCE) of 20.14 %. The research highlights the critical role of the dual transport layer structure in enhancing carrier separation and transport efficiency, providing valuable theoretical and experimental insights for the design and optimization of future high-performance solar cells.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766583","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}
We report regioselective bromination of meso-aryl 3-pyrrolyl BODIPY by introducing one to eight bromides at the pyrrole carbons of three pyrrole rings by treating meso-aryl 3-pyrrolyl BODIPY with N-bromosuccinimide/Br2 in CH2Cl2 under mild reaction conditions. The crystal structures obtained for five of these pyrrole brominated meso-aryl 3-pyrrolyl BODIPYs indicated that the appended pyrrolyl group adopts distortion from the 12-atom mean plane of the BODIPY and the maximum distortion of 40° was observed for octabrominated meso-aryl 3-pyrrolyl BODIPY. Upon increase of number of bromides from one to eight at the pyrrole carbons of meso-aryl 3-pyrrolyl BODIPY, the following key observations were made: (i) the absorption bands experiences bathochromic shift upto introduction of five bromides followed by hypsochromic shift from six to eight bromides indicating that the magnitude of absorption band shifts are non-additive; (ii) the fluorescence band experienced bathochromic shifts along with the decrease of quantum yield and singlet state lifetime; (iii) the electrochemical studies indicated that brominated 3-pyrrolyl BODIPYs are electron deficient and undergoes easier reductions with the increase of number of bromides at the pyrrole carbons of 3-pyrrolyl BODIPY. A linear additive relationship was noted between E1/2red and number of bromide groups at the pyrrole carbons of 3-pyrrolyl BODIPY and (iv) the halogenated 3-pyrrolyl BODIPYs are very efficient in generating singlet oxygen and the linear relationship was observed between singlet oxygen quantum yields and the number of bromides at the pyrrole carbons of 3-pyrrolyl BODIPY. DFT and TD-DFT studies supports the experimental observations.
{"title":"Synthesis, Structure, Spectral and Redox Properties of 3-Pyrrolyl BODIPYs Containing One to Eight Bromides at the Pyrrole Carbons","authors":"Pinky Chauhan, Mangalampalli Ravikanth","doi":"10.1039/d5dt00431d","DOIUrl":"https://doi.org/10.1039/d5dt00431d","url":null,"abstract":"We report regioselective bromination of meso-aryl 3-pyrrolyl BODIPY by introducing one to eight bromides at the pyrrole carbons of three pyrrole rings by treating meso-aryl 3-pyrrolyl BODIPY with N-bromosuccinimide/Br2 in CH2Cl2 under mild reaction conditions. The crystal structures obtained for five of these pyrrole brominated meso-aryl 3-pyrrolyl BODIPYs indicated that the appended pyrrolyl group adopts distortion from the 12-atom mean plane of the BODIPY and the maximum distortion of 40° was observed for octabrominated meso-aryl 3-pyrrolyl BODIPY. Upon increase of number of bromides from one to eight at the pyrrole carbons of meso-aryl 3-pyrrolyl BODIPY, the following key observations were made: (i) the absorption bands experiences bathochromic shift upto introduction of five bromides followed by hypsochromic shift from six to eight bromides indicating that the magnitude of absorption band shifts are non-additive; (ii) the fluorescence band experienced bathochromic shifts along with the decrease of quantum yield and singlet state lifetime; (iii) the electrochemical studies indicated that brominated 3-pyrrolyl BODIPYs are electron deficient and undergoes easier reductions with the increase of number of bromides at the pyrrole carbons of 3-pyrrolyl BODIPY. A linear additive relationship was noted between E1/2red and number of bromide groups at the pyrrole carbons of 3-pyrrolyl BODIPY and (iv) the halogenated 3-pyrrolyl BODIPYs are very efficient in generating singlet oxygen and the linear relationship was observed between singlet oxygen quantum yields and the number of bromides at the pyrrole carbons of 3-pyrrolyl BODIPY. DFT and TD-DFT studies supports the experimental observations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766582","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}
Lisa-Marie Servos, Hung Manh Tran, Nicolás Montesdeoca, Zisis Papadopoulos, Eun Sakong and Johannes Karges
Photodynamic therapy has garnered significant attention over the past decades for its potential in treating various types of cancer, as well as bacterial, fungal, and viral infections. However, current clinically approved photosensitizers based on a tetrapyrrolic scaffold face notable limitations, including low water solubility, slow body clearance, and photobleaching. As a promising alternative, Ru(II) polypyridyl complexes have emerged due to their favorable photophysical and biological properties (i.e., reactive oxygen species generation, high water solubility, and biocompatibility). Despite these attractive properties, the vast majority of compounds are associated with poor tumor accumulation, representing a major hurdle for therapeutic applications. To overcome this limitation, herein, the chemical synthesis and photophysical evaluation of the functionalization of a Ru(II) polypyridyl complex with an aldehyde group, as a synthetic precursor for further conjugation, is reported. To ensure that the intrinsic chemical reactivity of the aldehyde group remains unaffected by the coordination environment to the metal center, a phenyl spacer was strategically introduced between the central ligand framework and the aldehyde functionality. Computational studies indicated that upon excitation of the metal complex, an excited state electron from the ruthenium t2g orbital is transferred to the π* ligand orbital in a metal-to-ligand charge transfer transition. The compound was found to be highly stable under physiological conditions as well as upon irradiation. Upon light exposure, the metal complex was found to efficiently convert molecular oxygen to singlet oxygen. These findings highlight the potential of the aldehyde functionalized Ru(II) polypyridyl complex as a versatile precursor for photodynamic therapy.
{"title":"Functionalization of a Ru(ii) polypyridine complex with an aldehyde group as a synthetic precursor for photodynamic therapy†","authors":"Lisa-Marie Servos, Hung Manh Tran, Nicolás Montesdeoca, Zisis Papadopoulos, Eun Sakong and Johannes Karges","doi":"10.1039/D5DT00256G","DOIUrl":"10.1039/D5DT00256G","url":null,"abstract":"<p >Photodynamic therapy has garnered significant attention over the past decades for its potential in treating various types of cancer, as well as bacterial, fungal, and viral infections. However, current clinically approved photosensitizers based on a tetrapyrrolic scaffold face notable limitations, including low water solubility, slow body clearance, and photobleaching. As a promising alternative, Ru(<small>II</small>) polypyridyl complexes have emerged due to their favorable photophysical and biological properties (<em>i.e.</em>, reactive oxygen species generation, high water solubility, and biocompatibility). Despite these attractive properties, the vast majority of compounds are associated with poor tumor accumulation, representing a major hurdle for therapeutic applications. To overcome this limitation, herein, the chemical synthesis and photophysical evaluation of the functionalization of a Ru(<small>II</small>) polypyridyl complex with an aldehyde group, as a synthetic precursor for further conjugation, is reported. To ensure that the intrinsic chemical reactivity of the aldehyde group remains unaffected by the coordination environment to the metal center, a phenyl spacer was strategically introduced between the central ligand framework and the aldehyde functionality. Computational studies indicated that upon excitation of the metal complex, an excited state electron from the ruthenium t<small><sub>2g</sub></small> orbital is transferred to the π* ligand orbital in a metal-to-ligand charge transfer transition. The compound was found to be highly stable under physiological conditions as well as upon irradiation. Upon light exposure, the metal complex was found to efficiently convert molecular oxygen to singlet oxygen. These findings highlight the potential of the aldehyde functionalized Ru(<small>II</small>) polypyridyl complex as a versatile precursor for photodynamic therapy.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 16","pages":" 6411-6418"},"PeriodicalIF":3.5,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d5dt00256g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766573","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Katarina Ćeranić, Snezana D Zaric, Dusan P Malenov
Cation-π interactions between alkali, alkaline earth and ammonium cations and sandwich compounds of benzene and cyclopentadienyl anion were studied using quantum chemical CCSD(T)/CBS and DFT (B3LYP/def2-TZVP) calculations. The results show significantly stronger interactions of sandwich compounds with respect to (uncoordinated) benzene. Moreover, very strong cation-π interactions of cyclopentadienyl sandwich compounds are furthermore surpassed by cation-π interactions of benzene sandwich compound, which are capable of reaching remarkable interaction energy of -196.8 kcal/mol (Mg2+/W(benzene)2). While there are only small alterations of interaction energies for sandwich compounds of different transition metals (3d metals < 4d < 5d), cation-π interactions are highly dependent on the size and charge of cations (smaller and more charged cations forming stronger interactions), and they progressively become stronger in the following order: (uncoordinated) benzene < Cp sandwich < benzene sandwich. Aside from interaction energies, the cation-π interactions can be assesed by the means of their influence on geometries of sandwich compounds, which are found to strongly correlate with the strength of cation-π interactions. These results emphasize sandwich compounds, particularly those containing C6 aromatic rings, as promising candidates for new receptors for common metal cations.
{"title":"Cation recognition by benzene sandwich compounds – a DFT perspective","authors":"Katarina Ćeranić, Snezana D Zaric, Dusan P Malenov","doi":"10.1039/d5dt00395d","DOIUrl":"https://doi.org/10.1039/d5dt00395d","url":null,"abstract":"Cation-π interactions between alkali, alkaline earth and ammonium cations and sandwich compounds of benzene and cyclopentadienyl anion were studied using quantum chemical CCSD(T)/CBS and DFT (B3LYP/def2-TZVP) calculations. The results show significantly stronger interactions of sandwich compounds with respect to (uncoordinated) benzene. Moreover, very strong cation-π interactions of cyclopentadienyl sandwich compounds are furthermore surpassed by cation-π interactions of benzene sandwich compound, which are capable of reaching remarkable interaction energy of -196.8 kcal/mol (Mg2+/W(benzene)2). While there are only small alterations of interaction energies for sandwich compounds of different transition metals (3d metals < 4d < 5d), cation-π interactions are highly dependent on the size and charge of cations (smaller and more charged cations forming stronger interactions), and they progressively become stronger in the following order: (uncoordinated) benzene < Cp sandwich < benzene sandwich. Aside from interaction energies, the cation-π interactions can be assesed by the means of their influence on geometries of sandwich compounds, which are found to strongly correlate with the strength of cation-π interactions. These results emphasize sandwich compounds, particularly those containing C6 aromatic rings, as promising candidates for new receptors for common metal cations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758067","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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