Qi-Qi Jin, Xiao-Fang Duan, Dan-Ni Yan, Fan Yin, Chen-Chen Li, Lipeng Zhou, Li-Xuan Cai, Qing-Fu Sun
Stimulus-responsive luminescent metal-organic architectures have received a lot of attention in supramolecular chemistry. Herein, we report the synthesis of an acridine-based metal-organic macrocycle that undergoes reversible interconversion between monomer and dimer in response to variations in concentration and solvent, resulting in a switch between blue and green fluorescence. X-ray structure analysis reveals that hydrogen bonds between benzimidazole C-H and NO3- anions, along with π-π interactions between acridines are the primary driving forces behind this assembly behavior. The stimuli-responsive supramolecular fluorescence switch origins from the monomer and excimer states. The addition of 2,4,6-trinitrophenol (TNP) leads to a fluorescence “turn-off” at 430 nm for the monomer and a “turn-on” at 520 nm for the dimer, thus facilitating the ratiometric detection of TNP with detection limit as low as 13 ppb. Our work provides valuable insights into the construction of stimuli-responsive materials for fluorescence sensing.
{"title":"Stimuli-Responsive Dimeric Capsule Built from Acridine-Based Metallacycle for Ratiometric Fluorescence Sensing of TNP","authors":"Qi-Qi Jin, Xiao-Fang Duan, Dan-Ni Yan, Fan Yin, Chen-Chen Li, Lipeng Zhou, Li-Xuan Cai, Qing-Fu Sun","doi":"10.1039/d4dt03334e","DOIUrl":"https://doi.org/10.1039/d4dt03334e","url":null,"abstract":"Stimulus-responsive luminescent metal-organic architectures have received a lot of attention in supramolecular chemistry. Herein, we report the synthesis of an acridine-based metal-organic macrocycle that undergoes reversible interconversion between monomer and dimer in response to variations in concentration and solvent, resulting in a switch between blue and green fluorescence. X-ray structure analysis reveals that hydrogen bonds between benzimidazole C-H and NO<small><sub>3</sub></small><small><sup>-</sup></small> anions, along with π-π interactions between acridines are the primary driving forces behind this assembly behavior. The stimuli-responsive supramolecular fluorescence switch origins from the monomer and excimer states. The addition of 2,4,6-trinitrophenol (TNP) leads to a fluorescence “turn-off” at 430 nm for the monomer and a “turn-on” at 520 nm for the dimer, thus facilitating the ratiometric detection of TNP with detection limit as low as 13 ppb. Our work provides valuable insights into the construction of stimuli-responsive materials for fluorescence sensing.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"78 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401945","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}
Nalini Ravi, Prakash Kanapathi, S. Mohan, Tamilselvan Appadurai
Due to their superior optoelectronic properties, lead-free halide double perovskites (HDPs) have been extensively studied in a wide range of optoelectronic applications, especially in white light-emitting diodes (WLED). Focused on white light emission, the HDP structure’s dual octahedral configuration facilitates more lattice distortion, thereby fostering strong electron-phonon coupling derived self-trapped exciton (STE) emission upon photo-excitation. Herein, we propose to fabricate a highly feasible and easily fabricated phosphor-converted white light LED followed by an intensive pre-analysis of the structural, compositional and photophysical properties of the tri-cation mixed halide double perovskite. We have chosen the Cs2AgIn0.85Bi0.15Cl6 compound, as this composition exhibits high stability, direct-allowed transition, and notable photoluminescence quantum yield, which could be a potential candidate for electroluminescent based White light LED devices. However, we have incorporated lanthanide ion (Ce3+) into this cubic HDPs structure via tri-cation mixing at the B” site (Cs2AgIn0.85-XCeXBi0.15Cl6) to internally disturb the structural periodicity, and further enhance the STE emission. Initially, powder XRD revealed the lattice expansion induced by Ce3+ incorporation, XPS and TEM verified the substitution of Ce3+ at In3+site. Meanwhile compositional and optical studies have established the role of Ce3+ in retaining the direct allowed transition by effectively replacing the In3+site. The Urbach energy (EU), a measure of energetic disorderness at the band edges found to be significantly reduced value of 135 meV for Ce 5%. Most significantly, PL emission studies have shown an appreciable enhancement in the PL intensity with a prolonged STE lifetime of 670 ns for Cs2AgIn0.80Ce0.05Bi0.15Cl6, indicating the improved radiative recombination. Besides, excitation dependent Pl and PLE studies reveals that the emission is solely from STE states. Elaboratively, vibrational studies elucidated that Ce 5 % has restabilized elpasolite structure and enhanced the lattice phonons, which ultimately helped in boosting the STE emission as proven by Huang Rhys factor. Finally, an efficient and durable phosphor-converted WLED has been fabricated and its performance was assessed to exhibit CIE (0.35,0.32), CCT= 4368K, and an extremely high CRI, Ra= 92. Thus, our work provides an exclusive strategy to be employed to enhance the STE emission and applied potentially in electroluminescent-based WLED devices.
{"title":"Exploring the Structural and Photophysical properties of Tri-cation Mixed Halide Double Perovskite (Cs2AgIn0.85-XCeXBi0.15Cl6) for High Performance Phosphor-based WLED","authors":"Nalini Ravi, Prakash Kanapathi, S. Mohan, Tamilselvan Appadurai","doi":"10.1039/d4dt03417a","DOIUrl":"https://doi.org/10.1039/d4dt03417a","url":null,"abstract":"Due to their superior optoelectronic properties, lead-free halide double perovskites (HDPs) have been extensively studied in a wide range of optoelectronic applications, especially in white light-emitting diodes (WLED). Focused on white light emission, the HDP structure’s dual octahedral configuration facilitates more lattice distortion, thereby fostering strong electron-phonon coupling derived self-trapped exciton (STE) emission upon photo-excitation. Herein, we propose to fabricate a highly feasible and easily fabricated phosphor-converted white light LED followed by an intensive pre-analysis of the structural, compositional and photophysical properties of the tri-cation mixed halide double perovskite. We have chosen the Cs2AgIn0.85Bi0.15Cl6 compound, as this composition exhibits high stability, direct-allowed transition, and notable photoluminescence quantum yield, which could be a potential candidate for electroluminescent based White light LED devices. However, we have incorporated lanthanide ion (Ce3+) into this cubic HDPs structure via tri-cation mixing at the B” site (Cs2AgIn0.85-XCeXBi0.15Cl6) to internally disturb the structural periodicity, and further enhance the STE emission. Initially, powder XRD revealed the lattice expansion induced by Ce3+ incorporation, XPS and TEM verified the substitution of Ce3+ at In3+site. Meanwhile compositional and optical studies have established the role of Ce3+ in retaining the direct allowed transition by effectively replacing the In3+site. The Urbach energy (EU), a measure of energetic disorderness at the band edges found to be significantly reduced value of 135 meV for Ce 5%. Most significantly, PL emission studies have shown an appreciable enhancement in the PL intensity with a prolonged STE lifetime of 670 ns for Cs2AgIn0.80Ce0.05Bi0.15Cl6, indicating the improved radiative recombination. Besides, excitation dependent Pl and PLE studies reveals that the emission is solely from STE states. Elaboratively, vibrational studies elucidated that Ce 5 % has restabilized elpasolite structure and enhanced the lattice phonons, which ultimately helped in boosting the STE emission as proven by Huang Rhys factor. Finally, an efficient and durable phosphor-converted WLED has been fabricated and its performance was assessed to exhibit CIE (0.35,0.32), CCT= 4368K, and an extremely high CRI, Ra= 92. Thus, our work provides an exclusive strategy to be employed to enhance the STE emission and applied potentially in electroluminescent-based WLED devices.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401949","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}
A series of Cu(I) complexes supported by nitrogen-based tetradentate ligands were examined for their reactivity toward nitric oxide (NO). The copper complexes generated the corresponding Cu(II)-nitrite complexes in the presence of an excess molar amount of NO. Higher reactivity of the Cu(I) complex toward NO was observed with more negative Cu(I/II) redox potential, as their reactivity toward O2 and CO. [CuI(tepa)]+ with the most positive oxidation potential only reacts with NO among the diatomic gaseous molecule (NO, O2, and CO) examined in this study. DFT studies explained that the reactivity of Cu–NO complex is the key of the selectivity rather than its coordination bond stability.
{"title":"Reactivity of Copper(I) Complexes Supported by Tripodal Nitrogen-containing Tetradentate Ligands toward Gaseous Diatomic Molecules, NO, CO and O2","authors":"Yuma Morimoto, Keisuke Inoue, Shinobu Itoh","doi":"10.1039/d4dt03001j","DOIUrl":"https://doi.org/10.1039/d4dt03001j","url":null,"abstract":"A series of Cu(I) complexes supported by nitrogen-based tetradentate ligands were examined for their reactivity toward nitric oxide (NO). The copper complexes generated the corresponding Cu(II)-nitrite complexes in the presence of an excess molar amount of NO. Higher reactivity of the Cu(I) complex toward NO was observed with more negative Cu(I/II) redox potential, as their reactivity toward O<small><sub>2</sub></small> and CO. [Cu<small><sup>I</sup></small>(tepa)]<small><sup>+</sup></small> with the most positive oxidation potential only reacts with NO among the diatomic gaseous molecule (NO, O<small><sub>2</sub></small>, and CO) examined in this study. DFT studies explained that the reactivity of Cu–NO complex is the key of the selectivity rather than its coordination bond stability.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401943","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}
Rapid and sensitive detection of dopamine (DA) remains a great challenge in biosensing and disease diagnosis. In this work, we proposed a locking-in situ reduction series strategy for designing electrochemical DA sensor. Firstly, oxygen vacancy-enriched zeolite imidazole framework-8 (ZIF-8) was prepared by a facile solvothermal methods, and then Au nanoparticles (Au NPs) were encapsulated onto ZIF-8 (Au@ZIF-8) to obtain an efficient electrochemical DA sensor. The typical porous structure of ZIF-8 could prevent the aggregation and growth of the Au NPs, thereby improving the activity and stability of sensor. Under optimal test conditions, the sensor Au@ZIF-8 demonstrated remarkable electrochemical performance for DA detection, with high sensitivity (24.28 μA μM−1cm−2) in the linear range of 0.5-150 μM and low detection limit (0.003 μM, S/N=3). Furthermore, the sensor also exhibited good interference resistance and reproducibility. More importantly, DA from bovine serum samples was successfully detected on the sensor Au@ZIF-8. This study reveals that oxygen vacancy engineering and Au NPs could tune the electronic structure of the sensor and facilitate the adsorption and electrocatalytic oxidation of DA, showing great potential in the fabrication of biosensors.
{"title":"Oxygen Vacancy Enriched ZIF-8 Encapsulated Au Nanoparticles Boosts Electrochemical Dopamine Sensing","authors":"Dawei Yan, Xiaoxia Zhou, Xiaoqing Jia, shengke zhu, zizhao wang, Guisheng Li, Shige Wang","doi":"10.1039/d4dt03545c","DOIUrl":"https://doi.org/10.1039/d4dt03545c","url":null,"abstract":"Rapid and sensitive detection of dopamine (DA) remains a great challenge in biosensing and disease diagnosis. In this work, we proposed a locking-in situ reduction series strategy for designing electrochemical DA sensor. Firstly, oxygen vacancy-enriched zeolite imidazole framework-8 (ZIF-8) was prepared by a facile solvothermal methods, and then Au nanoparticles (Au NPs) were encapsulated onto ZIF-8 (Au@ZIF-8) to obtain an efficient electrochemical DA sensor. The typical porous structure of ZIF-8 could prevent the aggregation and growth of the Au NPs, thereby improving the activity and stability of sensor. Under optimal test conditions, the sensor Au@ZIF-8 demonstrated remarkable electrochemical performance for DA detection, with high sensitivity (24.28 μA μM−1cm−2) in the linear range of 0.5-150 μM and low detection limit (0.003 μM, S/N=3). Furthermore, the sensor also exhibited good interference resistance and reproducibility. More importantly, DA from bovine serum samples was successfully detected on the sensor Au@ZIF-8. This study reveals that oxygen vacancy engineering and Au NPs could tune the electronic structure of the sensor and facilitate the adsorption and electrocatalytic oxidation of DA, showing great potential in the fabrication of biosensors.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401948","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}
A fundamental understanding on the precise structural characteristic of interface active sites confined in heterogeneous catalysts is pivotal to construct vigorous metal–support boundary. Herein, a series of RhnV2O3–5– (n = 2–5) clusters were theoretically designed and we demonstrated that RhnV2O3–5– can catalytically reduce NO into N2 selectively by CO. We identified that the structure of RhnV2O3− can be considered as the dispersion of a Rhn moiety on the V2O3 “support” anchored by two V atoms. The distance between the top Rh atom that is responsible for reactant capture and V atom in RhnV2O3– becomes longer with the increase of cluster size, and the leading result is that V atoms in larger clusters can be less accessible during the reactions. A size-dependent behavior of NO reduction by RhnV2O3− was observed that V atom always be involved in the triatomic site RhV2 or Rh2V in Rh2−4V2O3− to drive N−O rupture and N−N coupling, while only three Rh atoms in Rh5V2O3− are available to drive NO reduction. One Rh atom in products Rh2−4V2O4,5− also functions as the anchoring site for CO and then delivers CO for oxidation by nearby coordinated oxygen atom. This finding emphasizes that our recently identified triatomic active site Ceδ+–Rhδ––Ceδ+ in RhCe2O3− for selective reduction of NO into N2 still prevails but could behave in different manners in larger RhnV2O3− (n ≥ 5) clusters.
{"title":"Size-dependent catalytic reactivity of NO Reduction by CO mediated by the RhnV2O3– clusters (n = 2–5)","authors":"Jin-You Chen, Hai Zhu, Tongmei Ma, Xiaona Li","doi":"10.1039/d4dt03118k","DOIUrl":"https://doi.org/10.1039/d4dt03118k","url":null,"abstract":"A fundamental understanding on the precise structural characteristic of interface active sites confined in heterogeneous catalysts is pivotal to construct vigorous metal–support boundary. Herein, a series of RhnV2O3–5– (n = 2–5) clusters were theoretically designed and we demonstrated that RhnV2O3–5– can catalytically reduce NO into N2 selectively by CO. We identified that the structure of RhnV2O3− can be considered as the dispersion of a Rhn moiety on the V2O3 “support” anchored by two V atoms. The distance between the top Rh atom that is responsible for reactant capture and V atom in RhnV2O3– becomes longer with the increase of cluster size, and the leading result is that V atoms in larger clusters can be less accessible during the reactions. A size-dependent behavior of NO reduction by RhnV2O3− was observed that V atom always be involved in the triatomic site RhV2 or Rh2V in Rh2−4V2O3− to drive N−O rupture and N−N coupling, while only three Rh atoms in Rh5V2O3− are available to drive NO reduction. One Rh atom in products Rh2−4V2O4,5− also functions as the anchoring site for CO and then delivers CO for oxidation by nearby coordinated oxygen atom. This finding emphasizes that our recently identified triatomic active site Ceδ+–Rhδ––Ceδ+ in RhCe2O3− for selective reduction of NO into N2 still prevails but could behave in different manners in larger RhnV2O3− (n ≥ 5) clusters.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"65 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393546","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}
Lanthanide-based single-ion magnets (Ln-SIMs) have garnered significant interest for their potential application in designing molecular-level information storage devices. Among various strategies to enhance magnetization blocking barriers in SIMs, synthesizing highly axially symmetric compounds is the most promising approach. In the present work, using state-of-the-art computational tools, we have thoroughly examined the electronic structure, bonding, and magnetic anisotropy in lanthanide mononitrides <strong>[LnN]</strong>(where Ln = Dy(III) and Tb(III)) and their encapsulation in zigzag boron nitride nanotubes (BNNT) of diameters (8,0) and (9,0) to design novel hybrid assemblies. Using periodic density functional theory calculations, we have thoroughly analyzed the structural and energetic perspective towards encapsulation of <strong>[LnN]</strong> molecules in parallel and perpendicular modes in BNNT(8,0) (<strong>8Ln</strong><small><sub>∥</sub></small> and <strong>8Ln</strong><small><sub>⊥</sub></small>) and BNNT(9,0) tubes (<strong>9Ln</strong><small><sub>∥</sub></small> and <strong>9Ln</strong><small><sub>⊥</sub></small>). Binding energy calculations suggest that the parallel arrangement of <strong>[LnN]</strong> is energetically more favorable (>30kJ/mol) than the perpendicular arrangement, with the BNNT(8,0) tube being energetically more preferred over the BNNT(9,0) tube. Non-covalent interaction plots clearly show dominant van der Waals stabilizing interaction in <strong>8Dy</strong><small><sub>∥</sub></small> and <strong>8Tb</strong><small><sub>∥</sub></small> compared to other assemblies. CASSCF calculations suggest that both the <strong>[DyN]</strong> and <strong>[TbN]</strong> show pure Ising type ground state with a giant barrier height of >1800 cm<small><sup>-1</sup></small> and strictly no ground state quantum tunneling of magnetization. CASSCF calculations predict that the <strong>8Dy</strong><small><sub>∥</sub></small> and <strong>8Tb</strong><small><sub>∥</sub></small> assemblies show record high <em>ab initio</em> blockade barrier (U<small><sub>cal</sub></small>) values of ~1707 and 1015 cm<small><sup>-1</sup></small>, respectively. Although <strong>9Dy</strong><small><sub>⊥</sub></small> is an energetically unfavorable mode, this orientation benefits from the tube’s crystal field, which leads to a U<small><sub>cal</sub></small> value of ~1939 cm<small><sup>-1</sup></small>, suggesting that encapsulation could further enhance the U<small><sub>cal</sub></small> values. Contrarily, the <strong>[TbN]</strong> molecules show a dramatic increase in the tunnel splitting values upon encapsulation in BNNT tubes, leading to a drastic decrease in U<small><sub>cal</sub></small> values. Our in-silico strategy offers insights into the magnetic anisotropy of simple <strong>[DyN]</strong> and <strong>[TbN]</strong> molecules and possible ways to integrate these molecules into BNNTs to generate hybrid magnetic material for information s
{"title":"Single-ion magnet behaviour in highly axial lanthanide mononitrides encapsulated in boron nitride nanotubes: a quantum chemical investigation","authors":"Kusum Kumari, Shruti Moorthy, Saurabh Kumar Singh","doi":"10.1039/d4dt03311f","DOIUrl":"https://doi.org/10.1039/d4dt03311f","url":null,"abstract":"Lanthanide-based single-ion magnets (Ln-SIMs) have garnered significant interest for their potential application in designing molecular-level information storage devices. Among various strategies to enhance magnetization blocking barriers in SIMs, synthesizing highly axially symmetric compounds is the most promising approach. In the present work, using state-of-the-art computational tools, we have thoroughly examined the electronic structure, bonding, and magnetic anisotropy in lanthanide mononitrides <strong>[LnN]</strong>(where Ln = Dy(III) and Tb(III)) and their encapsulation in zigzag boron nitride nanotubes (BNNT) of diameters (8,0) and (9,0) to design novel hybrid assemblies. Using periodic density functional theory calculations, we have thoroughly analyzed the structural and energetic perspective towards encapsulation of <strong>[LnN]</strong> molecules in parallel and perpendicular modes in BNNT(8,0) (<strong>8Ln</strong><small><sub>∥</sub></small> and <strong>8Ln</strong><small><sub>⊥</sub></small>) and BNNT(9,0) tubes (<strong>9Ln</strong><small><sub>∥</sub></small> and <strong>9Ln</strong><small><sub>⊥</sub></small>). Binding energy calculations suggest that the parallel arrangement of <strong>[LnN]</strong> is energetically more favorable (>30kJ/mol) than the perpendicular arrangement, with the BNNT(8,0) tube being energetically more preferred over the BNNT(9,0) tube. Non-covalent interaction plots clearly show dominant van der Waals stabilizing interaction in <strong>8Dy</strong><small><sub>∥</sub></small> and <strong>8Tb</strong><small><sub>∥</sub></small> compared to other assemblies. CASSCF calculations suggest that both the <strong>[DyN]</strong> and <strong>[TbN]</strong> show pure Ising type ground state with a giant barrier height of >1800 cm<small><sup>-1</sup></small> and strictly no ground state quantum tunneling of magnetization. CASSCF calculations predict that the <strong>8Dy</strong><small><sub>∥</sub></small> and <strong>8Tb</strong><small><sub>∥</sub></small> assemblies show record high <em>ab initio</em> blockade barrier (U<small><sub>cal</sub></small>) values of ~1707 and 1015 cm<small><sup>-1</sup></small>, respectively. Although <strong>9Dy</strong><small><sub>⊥</sub></small> is an energetically unfavorable mode, this orientation benefits from the tube’s crystal field, which leads to a U<small><sub>cal</sub></small> value of ~1939 cm<small><sup>-1</sup></small>, suggesting that encapsulation could further enhance the U<small><sub>cal</sub></small> values. Contrarily, the <strong>[TbN]</strong> molecules show a dramatic increase in the tunnel splitting values upon encapsulation in BNNT tubes, leading to a drastic decrease in U<small><sub>cal</sub></small> values. Our in-silico strategy offers insights into the magnetic anisotropy of simple <strong>[DyN]</strong> and <strong>[TbN]</strong> molecules and possible ways to integrate these molecules into BNNTs to generate hybrid magnetic material for information s","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"61 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393721","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}
Catherine E. Johnson, Mawuli Deegbey, Aleksandra Ilic, Nidhi Kaul, Om Prakash, Kenneth Wärnmark, Elena Jakubikova, Reiner Lomoth
A ferrous complex bearing tris(carbene)borate ligands with imidazol-2-ylidene donors has been characterized by experimental and computational methods. Despite the pronounced destabilization of metal centered states by the exceptionally σ-donating ligand, the high-energy 3MLCT state of [Fe(II)(phtmeimb)2] is rapidly deactivated by the barrierless conversion to the 3MC state.
{"title":"Shining light on the ferrous analogue: excited state dynamics of an Fe(II) hexa-carbene scorpionate complex","authors":"Catherine E. Johnson, Mawuli Deegbey, Aleksandra Ilic, Nidhi Kaul, Om Prakash, Kenneth Wärnmark, Elena Jakubikova, Reiner Lomoth","doi":"10.1039/d5dt00139k","DOIUrl":"https://doi.org/10.1039/d5dt00139k","url":null,"abstract":"A ferrous complex bearing tris(carbene)borate ligands with imidazol-2-ylidene donors has been characterized by experimental and computational methods. Despite the pronounced destabilization of metal centered states by the exceptionally σ-donating ligand, the high-energy <small><sup>3</sup></small>MLCT state of [Fe(<small>II</small>)(phtmeimb)<small><sub>2</sub></small>] is rapidly deactivated by the barrierless conversion to the <small><sup>3</sup></small>MC state.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"30 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393719","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}
yusi liu, Zhe-Kun Xu, Jia-Mei Zhang, Xiao-Gang Chen, Yan Qin, Zhong-Xia Wang
Hybrid perovskites possessing structural diversity and solution processability have been extensively studied in numerous application scenarios and either aroused significant interest in the design of high-performance molecular ferroelectric and ferroelastic materials. However, reports on the construction of three-dimensional (3D) perchlorate-based alkali metal hybrid perovskite molecular ferroelastics are scarce. Herein, dual-site substitution was implemented on the 3D non-perovskite network (MDABCO)K(ClO₄)₃ (MDABCO = N-methyl-N′-diazabicyclo[2.2.2]octonium) to achieve a series of 3D perchlorate-based alkali metal perovskite ferroelastics (FMDABCO)M(ClO₄)₃ (FMDABCO = N-fluoromethyl-N′-diazabicyclo[2.2.2]octonium, M = K, Rb, Cs). The H/F substitution on the organic motif of (MDABCO)K(ClO₄)₃ provides the significant structural transformation to a perovskite stacking of (FMDABCO)K(ClO₄)₃ accompanied by high-temperature structural phase transition and ferroelasticity. Through further substitutions on the alkali metals according to the fitted tolerance factor, (FMDABCO)Rb(ClO₄)₃ and (FMDABCO)Cs(ClO₄)₃ can not only maintain the 3D perovskite framework but also exhibit ferroelastic phase transitions at a higher temperature. Besides, (FMDABCO)Cs(ClO₄)₃ shows dual types of ferroelastic domain evolution with the Aizu notations of mmmF2/m and m3-mFmmm. This work offers great inspiration for the design of ferroelastic materials through rational chemical strategies.
{"title":"Three-dimensional perchlorate-based alkali metal hybrid perovskite molecular ferroelastic crystals","authors":"yusi liu, Zhe-Kun Xu, Jia-Mei Zhang, Xiao-Gang Chen, Yan Qin, Zhong-Xia Wang","doi":"10.1039/d4dt03416c","DOIUrl":"https://doi.org/10.1039/d4dt03416c","url":null,"abstract":"Hybrid perovskites possessing structural diversity and solution processability have been extensively studied in numerous application scenarios and either aroused significant interest in the design of high-performance molecular ferroelectric and ferroelastic materials. However, reports on the construction of three-dimensional (3D) perchlorate-based alkali metal hybrid perovskite molecular ferroelastics are scarce. Herein, dual-site substitution was implemented on the 3D non-perovskite network (MDABCO)K(ClO₄)₃ (MDABCO = N-methyl-N′-diazabicyclo[2.2.2]octonium) to achieve a series of 3D perchlorate-based alkali metal perovskite ferroelastics (FMDABCO)M(ClO₄)₃ (FMDABCO = N-fluoromethyl-N′-diazabicyclo[2.2.2]octonium, M = K, Rb, Cs). The H/F substitution on the organic motif of (MDABCO)K(ClO₄)₃ provides the significant structural transformation to a perovskite stacking of (FMDABCO)K(ClO₄)₃ accompanied by high-temperature structural phase transition and ferroelasticity. Through further substitutions on the alkali metals according to the fitted tolerance factor, (FMDABCO)Rb(ClO₄)₃ and (FMDABCO)Cs(ClO₄)₃ can not only maintain the 3D perovskite framework but also exhibit ferroelastic phase transitions at a higher temperature. Besides, (FMDABCO)Cs(ClO₄)₃ shows dual types of ferroelastic domain evolution with the Aizu notations of mmmF2/m and m3-mFmmm. This work offers great inspiration for the design of ferroelastic materials through rational chemical strategies.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"46 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393720","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}
Matthew D. Haynes, Andrea O'Reilly, Alice J. M. Poole, Aisling F. Roper, Stefan Thum, Louis J. Morris, Martyn P. Coles, J. Robin Fulton, Sjoerd Harder, Zoë R. Turner, Dermot O'Hare
The diverse solid-state structures and solution-phase dynamics of both neutral and heterometallic s-block “ate” complexes of the heavier alkaline earth metals (Ae; Ca–Ba) supported by a chelating and flexible di(amido)siloxane ligand ([<small><sup>NON-Dipp</sup></small>L]<small><sup>2−</sup></small> = [O(SiMe<small><sub>2</sub></small>NDipp)<small><sub>2</sub></small>]<small><sup>2−</sup></small>) are described, enabling comparison with those of closely related di(amido) ligands based on either flexible aliphatic or rigid xanthene-based backbones. Three dimeric alkaline earth complexes [(<small><sup>NON-Dipp</sup></small>L)Ae]<small><sub>2</sub></small> (Ae = Ca (<strong>2</strong>), Sr (<strong>3</strong>) and Ba (<strong>4</strong>)) which feature a κ<small><sup>3</sup></small>-N,O,N′-κ<small><sup>1</sup></small>-N′-tridentate coordination mode were prepared from protonolysis reactions between <small><sup>NON-Dipp</sup></small>LH<small><sub>2</sub></small> with <img align="middle" alt="Image ID:d5dt00044k-t1.gif" src="https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/DT/D5DT00044K/d5dt00044k-t1.gif"/> (Ae = Ca, Sr and Ba); N′′ = [N(SiMe<small><sub>3</sub></small>)<small><sub>2</sub></small>]<small><sup>−</sup></small>. In tetrahydrofuran, these complexes were readily converted into the monomeric adducts [(<small><sup>NON-Dipp</sup></small>L)Ae(thf)<small><sub><em>n</em></sub></small>] (<em>n</em> = 2, Ae = Ca (<strong>5</strong>); <em>n</em> = 3, Ae = Sr (<strong>6</strong>) and Ba (<strong>7</strong>)). Heterometallic Ae/K amide “ate” complexes were afforded through two routes: reaction of previously reported [(<small><sup>NON-Dipp</sup></small>L)Mg]<small><sub>2</sub></small> (<strong>1</strong>) with two equivalents of KN′′ at elevated temperatures resulted in [(<small><sup>NNO-Dipp</sup></small>L)Mg(μ-N′′)K]<small><sub><em>n</em></sub></small> (<strong>8</strong>; <small><sup>NNO-Dipp</sup></small>L = [OSiMe<small><sub>2</sub></small>NDippSiMe<small><sub>2</sub></small>NDipp]<small><sup>2−</sup></small>), whereas the equimolar reaction of <small><sup>NON-Dipp</sup></small>LH<small><sub>2</sub></small> with <img align="middle" alt="Image ID:d5dt00044k-t2.gif" src="https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/DT/D5DT00044K/d5dt00044k-t2.gif"/> led to [(<small><sup>NON-Dipp</sup></small>L)Ae(μ-N′′)K]<small><sub><em>n</em></sub></small> (Ae = Ca (<strong>9</strong>), Sr (<strong>10</strong>) and Ba (<strong>11</strong>)). Complexes <strong>8–11</strong> exist as one-dimensional coordination polymers propagated by K<small><sup>+</sup></small>–aryl π-facial interactions in the solid-state. The mixed amide/siloxide “NNO” ligand in <strong>8</strong> results from a 1,3-silyl retro-Brook rearrangement of the original di(amido)siloxane ligand, while the larger Ae<small><sup>2+</sup></small> congeners r
{"title":"Heavier alkaline earth and heterobimetallic s-block “ate” complexes of a di(amido)siloxane ligand: solid-state structure and dynamic solution-phase behaviour","authors":"Matthew D. Haynes, Andrea O'Reilly, Alice J. M. Poole, Aisling F. Roper, Stefan Thum, Louis J. Morris, Martyn P. Coles, J. Robin Fulton, Sjoerd Harder, Zoë R. Turner, Dermot O'Hare","doi":"10.1039/d5dt00044k","DOIUrl":"https://doi.org/10.1039/d5dt00044k","url":null,"abstract":"The diverse solid-state structures and solution-phase dynamics of both neutral and heterometallic s-block “ate” complexes of the heavier alkaline earth metals (Ae; Ca–Ba) supported by a chelating and flexible di(amido)siloxane ligand ([<small><sup>NON-Dipp</sup></small>L]<small><sup>2−</sup></small> = [O(SiMe<small><sub>2</sub></small>NDipp)<small><sub>2</sub></small>]<small><sup>2−</sup></small>) are described, enabling comparison with those of closely related di(amido) ligands based on either flexible aliphatic or rigid xanthene-based backbones. Three dimeric alkaline earth complexes [(<small><sup>NON-Dipp</sup></small>L)Ae]<small><sub>2</sub></small> (Ae = Ca (<strong>2</strong>), Sr (<strong>3</strong>) and Ba (<strong>4</strong>)) which feature a κ<small><sup>3</sup></small>-N,O,N′-κ<small><sup>1</sup></small>-N′-tridentate coordination mode were prepared from protonolysis reactions between <small><sup>NON-Dipp</sup></small>LH<small><sub>2</sub></small> with <img align=\"middle\" alt=\"Image ID:d5dt00044k-t1.gif\" src=\"https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/DT/D5DT00044K/d5dt00044k-t1.gif\"/> (Ae = Ca, Sr and Ba); N′′ = [N(SiMe<small><sub>3</sub></small>)<small><sub>2</sub></small>]<small><sup>−</sup></small>. In tetrahydrofuran, these complexes were readily converted into the monomeric adducts [(<small><sup>NON-Dipp</sup></small>L)Ae(thf)<small><sub><em>n</em></sub></small>] (<em>n</em> = 2, Ae = Ca (<strong>5</strong>); <em>n</em> = 3, Ae = Sr (<strong>6</strong>) and Ba (<strong>7</strong>)). Heterometallic Ae/K amide “ate” complexes were afforded through two routes: reaction of previously reported [(<small><sup>NON-Dipp</sup></small>L)Mg]<small><sub>2</sub></small> (<strong>1</strong>) with two equivalents of KN′′ at elevated temperatures resulted in [(<small><sup>NNO-Dipp</sup></small>L)Mg(μ-N′′)K]<small><sub><em>n</em></sub></small> (<strong>8</strong>; <small><sup>NNO-Dipp</sup></small>L = [OSiMe<small><sub>2</sub></small>NDippSiMe<small><sub>2</sub></small>NDipp]<small><sup>2−</sup></small>), whereas the equimolar reaction of <small><sup>NON-Dipp</sup></small>LH<small><sub>2</sub></small> with <img align=\"middle\" alt=\"Image ID:d5dt00044k-t2.gif\" src=\"https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/DT/D5DT00044K/d5dt00044k-t2.gif\"/> led to [(<small><sup>NON-Dipp</sup></small>L)Ae(μ-N′′)K]<small><sub><em>n</em></sub></small> (Ae = Ca (<strong>9</strong>), Sr (<strong>10</strong>) and Ba (<strong>11</strong>)). Complexes <strong>8–11</strong> exist as one-dimensional coordination polymers propagated by K<small><sup>+</sup></small>–aryl π-facial interactions in the solid-state. The mixed amide/siloxide “NNO” ligand in <strong>8</strong> results from a 1,3-silyl retro-Brook rearrangement of the original di(amido)siloxane ligand, while the larger Ae<small><sup>2+</sup></small> congeners r","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"65 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393717","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}
Kairui Yang, Zicheng Zhao, Jinyang Li, Xianglei Kong, Min Kou
The stable generation and structural characterization of sodium cationized nucleic acid radicals at the molecular level have always been a difficult problem to solve. Herein, we produced the radical cation of [Urd+Na-H]•+ through ultraviolet photodissociation (UVPD) of the precursor ion of [I-Urd+Na]+ in the gas phase and further studied its infrared multiphoton dissociation (IRMPD) spectrum in the region of 2750-3850 cm-1. The comparison between the IRMPD spectra of the precursor and radical cations shows their common features at both the 3445 and 3705 cm-1 peaks, as well as the difference at the 3628 cm-1 peak that exists only in the case of the latter. By combining with theoretical calculations, it is indicated that the bidentate coordination structure M-B(O2,O2')-1 and the tridentate coordination structure R-T(O2,O’,O5’)-(C5H-C1’)-1 are dominantly populated for the precursor and the radical cations, respectively. After the homo-cleavage of the C-I bond by the UV laser, a multi-step hydrogen transfer process started from the C1' position, followed by a rotation of the intramolecular C-N bond, resulting in the formation of the most stable isomer, characterized by its radical position at C1' and its tridentate coordination mode. This result indicates that the generation of free radicals of metal cationized nucleic acids by UVPD may result in the hydrogen transfer from the sugar ring, as well as the accompanied change of its coordination mode of the attached metal ions.
{"title":"Transition of the Coordination Modes in Sodiated Uridine Radicals Revealed by Infrared Multiphoton Dissociation Spectroscopy and Theoretical Calculations","authors":"Kairui Yang, Zicheng Zhao, Jinyang Li, Xianglei Kong, Min Kou","doi":"10.1039/d4dt03561e","DOIUrl":"https://doi.org/10.1039/d4dt03561e","url":null,"abstract":"The stable generation and structural characterization of sodium cationized nucleic acid radicals at the molecular level have always been a difficult problem to solve. Herein, we produced the radical cation of [Urd+Na-H]•+ through ultraviolet photodissociation (UVPD) of the precursor ion of [I-Urd+Na]+ in the gas phase and further studied its infrared multiphoton dissociation (IRMPD) spectrum in the region of 2750-3850 cm-1. The comparison between the IRMPD spectra of the precursor and radical cations shows their common features at both the 3445 and 3705 cm-1 peaks, as well as the difference at the 3628 cm-1 peak that exists only in the case of the latter. By combining with theoretical calculations, it is indicated that the bidentate coordination structure M-B(O2,O2')-1 and the tridentate coordination structure R-T(O2,O’,O5’)-(C5H-C1’)-1 are dominantly populated for the precursor and the radical cations, respectively. After the homo-cleavage of the C-I bond by the UV laser, a multi-step hydrogen transfer process started from the C1' position, followed by a rotation of the intramolecular C-N bond, resulting in the formation of the most stable isomer, characterized by its radical position at C1' and its tridentate coordination mode. This result indicates that the generation of free radicals of metal cationized nucleic acids by UVPD may result in the hydrogen transfer from the sugar ring, as well as the accompanied change of its coordination mode of the attached metal ions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"10 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393722","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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