Metallic interstitial compound Ni3Mo3N was synthesized as co-catalyst modified CdS nanorod for the first time. Photocatalytic studies show that the efficient charge separation and transfer from CdS to the Ni3Mo3N enables high visible-light-driven hydrogen evolution at 6.56 mmol·g-1·h-1. Schottky heterojunction between CdS and Ni3Mo3N might be the key factor for the high photocatalytic activity.
{"title":"Integration of Metallic interstitial co-catalyst (Ni3Mo3N) onto CdS nanorods accelerated charge separation and efficient photocatalytic hydrogen evolution","authors":"Lu Chen, Kaijie Zhang, yule sun, Ruowen Liang, Guiyang Yan, Renkun Huang","doi":"10.1039/d5dt02653a","DOIUrl":"https://doi.org/10.1039/d5dt02653a","url":null,"abstract":"Metallic interstitial compound Ni3Mo3N was synthesized as co-catalyst modified CdS nanorod for the first time. Photocatalytic studies show that the efficient charge separation and transfer from CdS to the Ni3Mo3N enables high visible-light-driven hydrogen evolution at 6.56 mmol·g-1·h-1. Schottky heterojunction between CdS and Ni3Mo3N might be the key factor for the high photocatalytic activity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"44 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145697146","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 demonstrate a mid-infrared (mid-IR) resonant optical tunneling platform that yields order-of-magnitude enhancement of the Goos--H"anchen (GH) shift through critical coupling in the transverse magnetic (TM) channel. The device comprises a prism, a monolayer graphene sheet, an ultrathin Weyl-semimetal (WSM, Co3Sn2S2) film and an air gap. The underlying mechanism is a balance between resonant tunneling across the gap and internal dissipation within the graphene/WSM stack, which drives a deep reflectance minimum and a rapid $pi$ phase winding and produces giant, sign controllable lateral displacements. At an incidence wavelength of $lambda=10.8 mumathrm{m}$, the structure operates very close to critical coupling ($R_{min}<0.5%$) and exhibits a steep TM reflection phase slope, which translates into a millimeter-scale lateral displacement of several hundred wavelengths ($10^{2}lambda$). The GH response is actively reconfigurable, and when the Fermi level of grephene is tuned to $u_c= 1.0~mathrm{eV}$, the tunneling can induce a sign reversal of the shift and a giant spike with $ 10^{3}lambda$. Filling the gap with an analyte further enables refractometric sensing with angular and amplitude sensitivities of $S_theta=25$--$38~mathrm{deg/RIU}$ and $S_D=(1.5$--$5)times10^{4},lambda/mathrm{RIU}$, respectively. These results establish mid-IR resonant tunneling as a compact route to ultra large, sign switchable GH shifts with clear utility for precision beam steering, weak measurement readout, and integrated photonic sensing.
{"title":"Giant Mid-Infrared Goos–Hänchen Shifts via Resonant Optical Tunneling in Graphene/Weyl-Semimetal Stacks","authors":"Ye Yang, Fenping Cui, Fenglin Xian, Gaige Zheng","doi":"10.1039/d5dt02701b","DOIUrl":"https://doi.org/10.1039/d5dt02701b","url":null,"abstract":"{We demonstrate a mid-infrared (mid-IR) resonant optical tunneling platform that yields order-of-magnitude enhancement of the Goos--H\"anchen (GH) shift through critical coupling in the transverse magnetic (TM) channel. The device comprises a prism, a monolayer graphene sheet, an ultrathin Weyl-semimetal (WSM, Co3Sn2S2) film and an air gap. The underlying mechanism is a balance between resonant tunneling across the gap and internal dissipation within the graphene/WSM stack, which drives a deep reflectance minimum and a rapid $pi$ phase winding and produces giant, sign controllable lateral displacements. At an incidence wavelength of $lambda=10.8 mumathrm{m}$, the structure operates very close to critical coupling ($R_{min}<0.5%$) and exhibits a steep TM reflection phase slope, which translates into a millimeter-scale lateral displacement of several hundred wavelengths ($10^{2}lambda$). The GH response is actively reconfigurable, and when the Fermi level of grephene is tuned to $u_c= 1.0~mathrm{eV}$, the tunneling can induce a sign reversal of the shift and a giant spike with $ 10^{3}lambda$. Filling the gap with an analyte further enables refractometric sensing with angular and amplitude sensitivities of $S_theta=25$--$38~mathrm{deg/RIU}$ and $S_D=(1.5$--$5)times10^{4},lambda/mathrm{RIU}$, respectively. These results establish mid-IR resonant tunneling as a compact route to ultra large, sign switchable GH shifts with clear utility for precision beam steering, weak measurement readout, and integrated photonic sensing.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"31 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704786","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}
Through introducing [Pd(PPh3)4] in to P73– solution, we have successfully synthesized and crystallized [Pd2(η4-P7)2]4– (1a) in [Na(crypt-222)]41a. As a phosphide congener of the reported [Pd2As14]4–, 1a can be viewed as a Pd2 dimer sandwiched by two (η4-P7) units, representing the first organic ligand free Pd-P cluster. In addition, 1a provides a platform for investigating Pd-P alloys on molecular level.
{"title":"[Pd2(η4-P7)2]4–: a Pd2 dimer sandwiched by two anionic nortricyclane-type polyphosphide","authors":"Fuxing Pan, Yu Tang, Minghao Deng, Xinyue Wang","doi":"10.1039/d5dt02437d","DOIUrl":"https://doi.org/10.1039/d5dt02437d","url":null,"abstract":"Through introducing [Pd(PPh3)4] in to P73– solution, we have successfully synthesized and crystallized [Pd2(η4-P7)2]4– (1a) in [Na(crypt-222)]41a. As a phosphide congener of the reported [Pd2As14]4–, 1a can be viewed as a Pd2 dimer sandwiched by two (η4-P7) units, representing the first organic ligand free Pd-P cluster. In addition, 1a provides a platform for investigating Pd-P alloys on molecular level.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"139 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704792","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}
In this study, we proposed modifying zinc gluconate with cardanol to prepare hard carbon, and the performance was improved compared with the existing hard carbon materials. After carbonization and acid etching, zinc gluconate and cardanol form a porous carbon structure with typical carbon layer crystallites. When preheated at 450 °C, cardanol and zinc gluconate were fully mixed to construct a hyper-crosslinked three-dimensional structure. At the same time, zinc oxide nanoparticles were formed and acted as a hard template to create nanopores in carbon frameworks during the following etching step. Then the porous mesophase carbon was further carbonized at 1000 °C to produce the typical hard carbons, which was named as Glu-CA-450-1000. Thanks to the rich carbon layers with suitable interlayer spacing and closed nanopores, Glu-CA-450-1000 exhibits excellent performances, with an initial coulombic efficiency (ICE) of 86 % and a reversible capacity of 365.8 mAh g−1 at 100 mA g−1. The "Glu-CA-450-1000" and Na3V2(PO4)3 (NVP) have been successfully assembled into a full battery. This study develops hard carbon using cardanol as a biomass carbon precursor and zinc gluconate as a bifunctional template, while revealing the importance of multistep calcination on the porous structure and carbon layer crystallites.
在本研究中，我们提出用腰果酚对葡萄糖酸锌进行改性制备硬碳，与现有的硬碳材料相比，性能得到了提高。葡萄糖酸锌和腰果酚经碳化和酸蚀后形成具有典型碳层晶体的多孔碳结构。在450℃下预热，腰果酚和葡萄糖酸锌充分混合，形成超交联的三维结构。同时，形成氧化锌纳米颗粒，并在接下来的蚀刻步骤中作为硬模板在碳框架中形成纳米孔。然后将多孔中间相碳在1000℃下进一步碳化，得到典型的硬碳，命名为Glu-CA-450-1000。由于含有丰富的碳层，层间间距合适，纳米孔封闭，Glu-CA-450-1000表现出优异的性能，初始库仑效率（ICE）为86%，在100 mA g -1下的可逆容量为365.8 mAh g -1。“Glu-CA-450-1000”和Na3V2(PO4)3 （NVP）已经成功组装成一个完整的电池。本研究以腰果酚为生物质碳前驱体，葡萄糖酸锌为双功能模板制备了硬碳，同时揭示了多步煅烧对多孔结构和碳层结晶的重要性。
{"title":"Cardanol Biomass-Derived Hard Carbon: A Promising Anode Material for Sodium-Ion Batteries","authors":"Weichen Li, xiang zheng, Luchao Yue, Zhi Wang, Chaohong Shi, Jing Tang","doi":"10.1039/d5dt02571k","DOIUrl":"https://doi.org/10.1039/d5dt02571k","url":null,"abstract":"In this study, we proposed modifying zinc gluconate with cardanol to prepare hard carbon, and the performance was improved compared with the existing hard carbon materials. After carbonization and acid etching, zinc gluconate and cardanol form a porous carbon structure with typical carbon layer crystallites. When preheated at 450 °C, cardanol and zinc gluconate were fully mixed to construct a hyper-crosslinked three-dimensional structure. At the same time, zinc oxide nanoparticles were formed and acted as a hard template to create nanopores in carbon frameworks during the following etching step. Then the porous mesophase carbon was further carbonized at 1000 °C to produce the typical hard carbons, which was named as Glu-CA-450-1000. Thanks to the rich carbon layers with suitable interlayer spacing and closed nanopores, Glu-CA-450-1000 exhibits excellent performances, with an initial coulombic efficiency (ICE) of 86 % and a reversible capacity of 365.8 mAh g−1 at 100 mA g−1. The \"Glu-CA-450-1000\" and Na3V2(PO4)3 (NVP) have been successfully assembled into a full battery. This study develops hard carbon using cardanol as a biomass carbon precursor and zinc gluconate as a bifunctional template, while revealing the importance of multistep calcination on the porous structure and carbon layer crystallites.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696955","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}
This study presents a comprehensive optical spectroscopic investigation of spin-crossover (SCO) behavior in the Fe(II) complex, [Fe(bppsipr)2](BF4)2 (where bppsipr = 4-(iso-propylsulfanyl)-2,6-bis(pyrazol-1-yl)pyridine), in both hydrated and dehydrated single-crystal forms. High-resolution single-crystal UV-Vis absorption spectroscopy is employed to monitor thermally driven spin-state switching at multiple temperature scan rates, revealing abrupt transitions with variable hysteresis widths. In the hydrated form, hysteresis width narrowed with decreasing scan rate due to reduced kinetic barriers and variation in cooperativity. In contrast, the dehydrated form displayed stronger scan-rate dependence, wider hysteresis, and metastable high-spin (HS) stabilization upon cooling, attributed to increased lattice rigidity, and elevated relaxation barriers. Notably, the mutual interplay between elastic and magnetic interactions differ between cooling (HS → LS) and heating (LS → HS) cycles across scan rates. Thermal annealing of the dehydrated crystal restored structural homogeneity, yielding narrower hysteresis and upward-shifted transition temperatures during cooling, without affecting the heating branch—indicating asymmetric energy dissipation dynamics (magnetic vs elastic) during HS → LS and LS → HS transitions. The hydrated compound also demonstrates efficient photoinduced LS → HS switching (LIESST) at 4 K, with metastable HS state relaxing sharply near T(LIESST). Time-resolved spectroscopy between 50-75 K revealed two-step HS → LS relaxation mechanism, involving initial stochastic LS nucleation followed by cooperative domain growth. In contrast, no photoresponse is observed in the dehydrated form within measurement timeframe, likely due to increased ΔE0HL and higher lattice stiffness. Partial LS recovery via reverse-LIESST (830 nm excitation) confirms bistability and domain sensitivity in the hydrated state. To model the photoinduced relaxation behavior, an advanced mechanoelastic framework is applied, integrating thermodynamic, elastic, and local structural factors including hydration-induced pressure and Jahn–Teller distortion. The model successfully reproduced the cooperative HS → LS relaxation kinetics and domain evolution, validating the significance of local pressure fluctuations, lattice inhomogeneities, and angular-strain in dictating SCO dynamics. Overall, this work highlights the critical influence of hydration-dehydration, lattice quality, and thermal history on spin-state cooperativity and bistability, offering deep insight into the molecular control of SCO behavior. The integrated experimental–theoretical approach offers valuable insights for designing next-generation photoresponsive SCO materials with tunable switching characteristics.
{"title":"Optical Signatures of Hydration-Controlled Hysteretic Spin-crossover in Single Crystals of an Fe(II) Complex","authors":"Chinmoy Das, Malcolm Halcrow, Denisa Coltuneac, Laurentiu Stoleriu, Pradip Chakraborty","doi":"10.1039/d5dt02247a","DOIUrl":"https://doi.org/10.1039/d5dt02247a","url":null,"abstract":"This study presents a comprehensive optical spectroscopic investigation of spin-crossover (SCO) behavior in the Fe(II) complex, [Fe(bppsipr)2](BF4)2 (where bppsipr = 4-(iso-propylsulfanyl)-2,6-bis(pyrazol-1-yl)pyridine), in both hydrated and dehydrated single-crystal forms. High-resolution single-crystal UV-Vis absorption spectroscopy is employed to monitor thermally driven spin-state switching at multiple temperature scan rates, revealing abrupt transitions with variable hysteresis widths. In the hydrated form, hysteresis width narrowed with decreasing scan rate due to reduced kinetic barriers and variation in cooperativity. In contrast, the dehydrated form displayed stronger scan-rate dependence, wider hysteresis, and metastable high-spin (HS) stabilization upon cooling, attributed to increased lattice rigidity, and elevated relaxation barriers. Notably, the mutual interplay between elastic and magnetic interactions differ between cooling (HS → LS) and heating (LS → HS) cycles across scan rates. Thermal annealing of the dehydrated crystal restored structural homogeneity, yielding narrower hysteresis and upward-shifted transition temperatures during cooling, without affecting the heating branch—indicating asymmetric energy dissipation dynamics (magnetic vs elastic) during HS → LS and LS → HS transitions. The hydrated compound also demonstrates efficient photoinduced LS → HS switching (LIESST) at 4 K, with metastable HS state relaxing sharply near T(LIESST). Time-resolved spectroscopy between 50-75 K revealed two-step HS → LS relaxation mechanism, involving initial stochastic LS nucleation followed by cooperative domain growth. In contrast, no photoresponse is observed in the dehydrated form within measurement timeframe, likely due to increased ΔE0HL and higher lattice stiffness. Partial LS recovery via reverse-LIESST (830 nm excitation) confirms bistability and domain sensitivity in the hydrated state. To model the photoinduced relaxation behavior, an advanced mechanoelastic framework is applied, integrating thermodynamic, elastic, and local structural factors including hydration-induced pressure and Jahn–Teller distortion. The model successfully reproduced the cooperative HS → LS relaxation kinetics and domain evolution, validating the significance of local pressure fluctuations, lattice inhomogeneities, and angular-strain in dictating SCO dynamics. Overall, this work highlights the critical influence of hydration-dehydration, lattice quality, and thermal history on spin-state cooperativity and bistability, offering deep insight into the molecular control of SCO behavior. The integrated experimental–theoretical approach offers valuable insights for designing next-generation photoresponsive SCO materials with tunable switching characteristics.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"115 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689135","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}
Svetlana V. Baryshnikova, Polina Shisterova, Maxim V. Arsenyev, Irina N Meshcheryakova, Dmitry S. Kolevatov, Ilya Yakushev, Rinat R. Aysin, Tatyana N Kocherova, Alexandr Vladimirovich Piskunov
New antimony(V) complexes, 1 and 2, containing the redox-active ligands N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine (LH4) and glyoxal-bis(2-hydroxy-3,5-di-tert-butylanil) (L’H2), respectively, were synthesized and characterized. Single-crystal X-ray diffraction analysis determined that complexes 1 and 2 exhibit a distorted pentagonal bipyramidal structure. These complexes contain a tetradentate, redox-active ONNO ligand that, doubly deprotonated, forms a dianion with a nearly planar core. The UV/vis/NIR absorption spectra of 1 and 2 demonstrate intense bands in the of 500 - 1000 nm range attributed to intraligand charge transfer (ILCT). Electrochemical analysis demonstrates the redox-amphoteric properties of complexes 1 and 2. Complex 1 also exhibits efficient photothermal conversion (η = 57%) under 808 nm laser irradiation.
{"title":"Antimony(V) complexes with a tetradentate ONNO redox-active ligands. Optical, electrochemical and photothermal properties","authors":"Svetlana V. Baryshnikova, Polina Shisterova, Maxim V. Arsenyev, Irina N Meshcheryakova, Dmitry S. Kolevatov, Ilya Yakushev, Rinat R. Aysin, Tatyana N Kocherova, Alexandr Vladimirovich Piskunov","doi":"10.1039/d5dt02666k","DOIUrl":"https://doi.org/10.1039/d5dt02666k","url":null,"abstract":"New antimony(V) complexes, 1 and 2, containing the redox-active ligands N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine (LH4) and glyoxal-bis(2-hydroxy-3,5-di-tert-butylanil) (L’H2), respectively, were synthesized and characterized. Single-crystal X-ray diffraction analysis determined that complexes 1 and 2 exhibit a distorted pentagonal bipyramidal structure. These complexes contain a tetradentate, redox-active ONNO ligand that, doubly deprotonated, forms a dianion with a nearly planar core. The UV/vis/NIR absorption spectra of 1 and 2 demonstrate intense bands in the of 500 - 1000 nm range attributed to intraligand charge transfer (ILCT). Electrochemical analysis demonstrates the redox-amphoteric properties of complexes 1 and 2. Complex 1 also exhibits efficient photothermal conversion (η = 57%) under 808 nm laser irradiation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"115 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689136","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}
Frustrated Lewis pairs (FLPs) have emerged as versatile metal-free catalysts for small-molecule activation, and strategies to control frustration through geometric immobilization and electronic tuning remain a topic of significant interest. Carborane cages, with their unique coordination-dependent electronic effects, have recently been shown to modulate FLP frustration. In this work, we introduce o-silaborane cages, whose coordination-based electronic effects had not previously been explored for modulating FLP reactivity. The –BH2 and –PH2 substituents were strategically placed at distinct coordinating sites of the cages to systematically compare the coordination dichotomy of o-carborane and o-silaborane frameworks in influencing the frustration of Lewis pairs. CO2 activation was employed as the model reaction to assess and compare these effects. Electronic structure analysis reveals that silaborane exerts stronger electron-withdrawing and electron-donating influences than carborane, leading to pronounced differences in acidity–basicity balance, strain distribution, and the stability of CO2 complexes. Furthermore, transition-state energetics demonstrate that site-dependent positioning of Lewis acid–base centres critically governs activation barriers. In the o-carborane framework, the acid and base groups positioned at the 1,4-sites exhibit the highest reactivity, whereas in the o-silaborane system, the 4,9-substituted arrangement is identified as the most reactive. These findings establish silaborane as a promising bridging unit, opening new design pathways for tuneable FLP-based CO2 utilization and broader small-molecule activation.
{"title":"Can Silaborane Serve as an Effective Bridging Unit for Lewis Pairs? A Comparative Discourse with Carborane","authors":"Mohmmad Faizan, Zaid Malik, Sandhya Madem, Ravinder Pawar","doi":"10.1039/d5dt02382c","DOIUrl":"https://doi.org/10.1039/d5dt02382c","url":null,"abstract":"Frustrated Lewis pairs (FLPs) have emerged as versatile metal-free catalysts for small-molecule activation, and strategies to control frustration through geometric immobilization and electronic tuning remain a topic of significant interest. Carborane cages, with their unique coordination-dependent electronic effects, have recently been shown to modulate FLP frustration. In this work, we introduce o-silaborane cages, whose coordination-based electronic effects had not previously been explored for modulating FLP reactivity. The –BH2 and –PH2 substituents were strategically placed at distinct coordinating sites of the cages to systematically compare the coordination dichotomy of o-carborane and o-silaborane frameworks in influencing the frustration of Lewis pairs. CO2 activation was employed as the model reaction to assess and compare these effects. Electronic structure analysis reveals that silaborane exerts stronger electron-withdrawing and electron-donating influences than carborane, leading to pronounced differences in acidity–basicity balance, strain distribution, and the stability of CO2 complexes. Furthermore, transition-state energetics demonstrate that site-dependent positioning of Lewis acid–base centres critically governs activation barriers. In the o-carborane framework, the acid and base groups positioned at the 1,4-sites exhibit the highest reactivity, whereas in the o-silaborane system, the 4,9-substituted arrangement is identified as the most reactive. These findings establish silaborane as a promising bridging unit, opening new design pathways for tuneable FLP-based CO2 utilization and broader small-molecule activation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"54 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689142","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 effect of the very small anisotropy on the slow relaxation of the magnetization has been analysed for two series of structurally related MnII complexes with trans-octahedral or trigonal bipyramid environment. Complexes with formula [MnX2(S,S-L1)] in which L1 is a neutral tetradentate Schiff base and X = NCS- (1NCS) , Cl- (2Cl), Br- (3Br), I- (4I) and [MnX2(L2)] in which L2 is a neutral tridentate Schiff base and X = Cl- (5Cl), Br- (6Br) and the 1D [Mn(N3)2(L2)]n (7) systems were characterized. Profiting the increasing Spin Orbit Coupling (SOC) contribution of the heavier halide donors in complexes 1-6 the gradation of the axial zero field splitting parameter (D) comprised between ~0.1-0.6 cm-1, determined from EPR spectroscopy, has been studied. Alter current measurements show that the slow relaxation of the magnetization vanishes for the larger D values, evidencing the crucial effect of D values ~ 0.2 cm-1.
{"title":"Probing the need of a very low axial zero field splitting in MnII systems with slow relaxation of the magnetization","authors":"Evangelos Pilichos, Julia Mayans, Albert Escuer","doi":"10.1039/d5dt02349a","DOIUrl":"https://doi.org/10.1039/d5dt02349a","url":null,"abstract":"The effect of the very small anisotropy on the slow relaxation of the magnetization has been analysed for two series of structurally related MnII<small><sup></sup></small> complexes with trans-octahedral or trigonal bipyramid environment. Complexes with formula [MnX<small><sub>2</sub></small>(S,S-L1)] in which L1 is a neutral tetradentate Schiff base and X = NCS- (<strong>1</strong><small><sub>NCS</sub></small>) , Cl- (<strong>2</strong><small><sub>Cl</sub></small>), Br- (<strong>3</strong><small><sub>Br</sub></small>), I- (<strong>4</strong><small><sub>I</sub></small>) and [MnX<small><sub>2</sub></small>(L2)] in which L2 is a neutral tridentate Schiff base and X = Cl- (<strong>5</strong><small><sub>Cl</sub></small>), Br- (<strong>6</strong><small><sub>Br</sub></small>) and the 1D [Mn(N<small><sub>3</sub></small>)<small><sub>2</sub></small>(L2)]<small><sub>n</sub></small> (<strong>7</strong>) systems were characterized. Profiting the increasing Spin Orbit Coupling (SOC) contribution of the heavier halide donors in complexes <strong>1</strong>-<strong>6</strong> the gradation of the axial zero field splitting parameter (D) comprised between ~0.1-0.6 cm<small><sup>-1</sup></small>, determined from EPR spectroscopy, has been studied. Alter current measurements show that the slow relaxation of the magnetization vanishes for the larger D values, evidencing the crucial effect of D values ~ 0.2 cm<small><sup>-1</sup></small>.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"54 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689134","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}
Nour Shalhoub, Edoardo Marchini, Federico Coppola, Roberto Argazzi, Stefano Caramori, Mariachiara Pastore, Philippe Pierrat, Philippe C Gros
Correction for 'Tuning the electronic properties of Fe(II)-NHC sensitizers with thienyl π-extended ligands' by Nour Shalhoub et al., Dalton Trans., 2025, 54, 17662-17673, https://doi.org/10.1039/d5dt02301g.
{"title":"Correction: Tuning the electronic properties of Fe(II)-NHC sensitizers with thienyl π-extended ligands.","authors":"Nour Shalhoub, Edoardo Marchini, Federico Coppola, Roberto Argazzi, Stefano Caramori, Mariachiara Pastore, Philippe Pierrat, Philippe C Gros","doi":"10.1039/d5dt90212f","DOIUrl":"https://doi.org/10.1039/d5dt90212f","url":null,"abstract":"<p><p>Correction for 'Tuning the electronic properties of Fe(II)-NHC sensitizers with thienyl π-extended ligands' by Nour Shalhoub <i>et al.</i>, <i>Dalton Trans.</i>, 2025, <b>54</b>, 17662-17673, https://doi.org/10.1039/d5dt02301g.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145675802","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}
In this study, a ThT@Q[8] host-guest complex was obtained via an interaction between cucurbit[8]uril (Q[8]) as the host and thioflavin T (ThT) as the guest. Then, ThT@Q[8]-Fe3+ and ThT@Q[8]-Hg2+ fluorescent probes were constructed based on metal ion stimuli-responsive supramolecular interactions. These probes exhibited distinct fluorescence responses toward five physiological phosphate anions (Pi, PPi, AMP, ADP, and ATP) due to electrostatic and coordinative interactions. A supramolecular fluorescence sensing array was thus developed using ThT@Q[8]-Fe3+ and ThT@Q[8]-Hg2+ as sensing units for the discrimination and detection of these phosphate anions. The array showed excellent anti-interference performance and successfully distinguished phosphate anions at low, medium, and high concentrations. A good linear relationship was observed between Factor 1 and anion concentration over the range from the limit of quantitation (LOQ) to 10 μM, with a limit of detection (LOD) as low as 0.13 μM. The array was also effective in discriminating the five phosphate anions in human serum. With advantages such as rich output signals, low cost, and simple preparation, this array holds considerable potential for detecting phosphate anions in biological systems. Furthermore, it enabled monitoring of ATP hydrolysis and evaluation of the energy charge in human serum.
{"title":"Cucurbit[8]uril-guest-metal ion self-assemblies as fluorescence sensor arrays for discrimination and detection of physiological phosphates.","authors":"Ru-Pei Yang,Hong-Xue Wang,Qing Tang,Jian-Hang Hu,Hong-Ling Yi,Hong-Yuan Hu,Zhu Tao,Ying Huang","doi":"10.1039/d5dt02054a","DOIUrl":"https://doi.org/10.1039/d5dt02054a","url":null,"abstract":"In this study, a ThT@Q[8] host-guest complex was obtained via an interaction between cucurbit[8]uril (Q[8]) as the host and thioflavin T (ThT) as the guest. Then, ThT@Q[8]-Fe3+ and ThT@Q[8]-Hg2+ fluorescent probes were constructed based on metal ion stimuli-responsive supramolecular interactions. These probes exhibited distinct fluorescence responses toward five physiological phosphate anions (Pi, PPi, AMP, ADP, and ATP) due to electrostatic and coordinative interactions. A supramolecular fluorescence sensing array was thus developed using ThT@Q[8]-Fe3+ and ThT@Q[8]-Hg2+ as sensing units for the discrimination and detection of these phosphate anions. The array showed excellent anti-interference performance and successfully distinguished phosphate anions at low, medium, and high concentrations. A good linear relationship was observed between Factor 1 and anion concentration over the range from the limit of quantitation (LOQ) to 10 μM, with a limit of detection (LOD) as low as 0.13 μM. The array was also effective in discriminating the five phosphate anions in human serum. With advantages such as rich output signals, low cost, and simple preparation, this array holds considerable potential for detecting phosphate anions in biological systems. Furthermore, it enabled monitoring of ATP hydrolysis and evaluation of the energy charge in human serum.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"93 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680718","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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