In this work, 4-((4-methylbenzyl)oxy)benzaldehyde resin-supported Pd(II)-Schiff base PS@Pd(OAc)2 was synthesized. FT-IR, XPS, TGA, ICP-MS, and powder XRD established the structure of PS@Pd(OAc)2. The morphology and distribution of elements on PS@Pd(OAc)2 were determined using SEM, TEM, and elemental mapping analysis. The heterogenized PS@Pd(OAc)2 catalyst was found to be efficient in promoting three-component Mizoroki–Heck coupling via an in situ Witting reaction, where (E)-1,2-diphenylethenes were efficiently synthesized from the Witting salt. In this one-pot reaction, this catalyst exhibits a distinct synergistic effect. The significant mass-transfer limitation results from a nonsignificant distribution of active sites amalgamated with the crumpling of catalysts, which facilitates the smooth, easy movement of the reactants and products toward the well-spaced active catalytic sites on the catalyst's surface. These characteristics increase the catalytic activity of PS@Pd(OAc)2. Moreover, the catalyst was found to be quite robust for this reaction with very little metal leaching; thus, it can be efficiently recycled. Hence, multiple uses were established, and its reusability was proven in this important reaction.
{"title":"Immobilization of palladium(II) acetate on a polymer-anchored Schiff base as a new heterogeneous catalyst for three-component one-Pot Mizoroki–Heck coupling via an in situ witting reaction","authors":"Akash V. Gujarati, Divyesh K. Patel","doi":"10.1039/d4dt03509g","DOIUrl":"https://doi.org/10.1039/d4dt03509g","url":null,"abstract":"In this work, 4-((4-methylbenzyl)oxy)benzaldehyde resin-supported Pd<small><sup>(II)</sup></small>-Schiff base PS@Pd(OAc)<small><sub>2</sub></small> was synthesized. FT-IR, XPS, TGA, ICP-MS, and powder XRD established the structure of PS@Pd(OAc)<small><sub>2</sub></small>. The morphology and distribution of elements on PS@Pd(OAc)<small><sub>2</sub></small> were determined using SEM, TEM, and elemental mapping analysis. The heterogenized PS@Pd(OAc)<small><sub>2</sub></small> catalyst was found to be efficient in promoting three-component Mizoroki–Heck coupling <em>via</em> an <em>in situ</em> Witting reaction, where (<em>E</em>)-1,2-diphenylethenes were efficiently synthesized from the Witting salt. In this one-pot reaction, this catalyst exhibits a distinct synergistic effect. The significant mass-transfer limitation results from a nonsignificant distribution of active sites amalgamated with the crumpling of catalysts, which facilitates the smooth, easy movement of the reactants and products toward the well-spaced active catalytic sites on the catalyst's surface. These characteristics increase the catalytic activity of PS@Pd(OAc)<small><sub>2</sub></small>. Moreover, the catalyst was found to be quite robust for this reaction with very little metal leaching; thus, it can be efficiently recycled. Hence, multiple uses were established, and its reusability was proven in this important reaction.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"55 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375800","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}
N-Salicylideneaminopyridine (SAP) is a well-known organic chromic compound that show reversible colour change upon UV light irradiation (photochromism) and upon cooling (thermochromism). Herein, we report novel multi-chromic metal complexes containing SAP derivatives as ligands, viz. [Ni(NCS)2(3,5-t-Bu-SAP)4] (Ni1) and [Co(NCS)2(3,5-t-Bu-SAP)4] (Co1). The Ni1 crystals exhibited both photo- and thermochromism with new colour variations, which were due to the light absorption of the Ni(II) ions and chromic properties of the SAP ligands. The Co1 crystal also exhibited photo- and thermochromism originating from the SAP ligands. Furthermore, the Co1 crystal exhibited mechanochromism induced by grinding with a mortar, which was considered to be attributable to the deformation of the Co1 coordination geometry. Such triple-chromic material is rare and much fascinating for the applications of multiple sensors, memory devices, and functional inks.
{"title":"Triple-chromic (Photo-, Thermo-, and Mechano-chromic) Metal Complexes Containing N-Salicylideneaminopyridine Ligands","authors":"Haruki Sugiyama, Atsuko Arita, Akiko Sekine, Hidehiro Uekusa","doi":"10.1039/d4dt01755b","DOIUrl":"https://doi.org/10.1039/d4dt01755b","url":null,"abstract":"<em>N</em>-Salicylideneaminopyridine (SAP) is a well-known organic chromic compound that show reversible colour change upon UV light irradiation (photochromism) and upon cooling (thermochromism). Herein, we report novel multi-chromic metal complexes containing SAP derivatives as ligands, viz. [Ni(NCS)2(3,5-t-Bu-SAP)4] (<strong>Ni1</strong>) and [Co(NCS)2(3,5-t-Bu-SAP)4] (<strong>Co1)</strong>. The <strong>Ni1</strong> crystals exhibited both photo- and thermochromism with new colour variations, which were due to the light absorption of the Ni(II) ions and chromic properties of the SAP ligands. The <strong>Co1</strong> crystal also exhibited photo- and thermochromism originating from the SAP ligands. Furthermore, the <strong>Co1</strong> crystal exhibited mechanochromism induced by grinding with a mortar, which was considered to be attributable to the deformation of the <strong>Co1</strong> coordination geometry. Such triple-chromic material is rare and much fascinating for the applications of multiple sensors, memory devices, and functional inks.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258416","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}
Patrick D. F. Murton, Christiane Timmel, Stuart R Mackenzie, Patricia Rodriguez Macia
Ferricyanide is commonly used as a reoxidant in photochemical studies of redox proteins including cytochromes, photosystem II and flavoproteins. A low-spin d5 complex, [Fe(III)(CN)6]3− is a powerful electron acceptor which efficiently reoxidises photo-generated radical species. Unfortunately, ferricyanide itself absorbs strongly in the blue and a better understanding of its own photochemistry is required. Here, we present a combined UV/Vis and infrared spectroscopic study of the blue light photo-induced degradation of ferricyanide under conditions commonly employed in photochemical studies of proteins. Clear differences are observed in the photochemistry in pure water, Tris buffer and 20% glycerol solution, which are interpreted in terms of solvent-ligand exchange and ligand to metal charge transfer. The implications for photochemical studies of proteins employing ferricyanide as a reoxidant are discussed.
{"title":"Blue-light photodegradation of ferricyanide under protein relevant conditions †","authors":"Patrick D. F. Murton, Christiane Timmel, Stuart R Mackenzie, Patricia Rodriguez Macia","doi":"10.1039/d4dt02916j","DOIUrl":"https://doi.org/10.1039/d4dt02916j","url":null,"abstract":"Ferricyanide is commonly used as a reoxidant in photochemical studies of redox proteins including cytochromes, photosystem II and flavoproteins. A low-spin d5<small><sup></sup></small> complex, [Fe(III)(CN)6<small><sub></sub></small>]3−<small><sup></sup></small> is a powerful electron acceptor which efficiently reoxidises photo-generated radical species. Unfortunately, ferricyanide itself absorbs strongly in the blue and a better understanding of its own photochemistry is required. Here, we present a combined UV/Vis and infrared spectroscopic study of the blue light photo-induced degradation of ferricyanide under conditions commonly employed in photochemical studies of proteins. Clear differences are observed in the photochemistry in pure water, Tris buffer and 20% glycerol solution, which are interpreted in terms of solvent-ligand exchange and ligand to metal charge transfer. The implications for photochemical studies of proteins employing ferricyanide as a reoxidant are discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"62 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258410","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}
Xuban Gastearena, Jon Mattin Matxain, Fernando Ruipérez
The activation of dinitrogen (N2) is a crucial step in synthesizing nitrogen-based compounds and remains a significant challenge due to its strong triple bond. Currently, industrial N2 conversion relies on the Haber-Bosch process, a highly energy-intensive method that utilizes transition metal-based catalysts. Frustrated Lewis pairs (FLPs) have emerged as a promising alternative for N2 activation without the need for transition metals. In this work, we employ density functional theory (DFT) to investigate the activation of N2 by transition metal-free Lewis acids (LAs) and bases (LBs). Our study demonstrates that LAs play a crucial role in capturing N2 and determining the thermodynamics of activation, while LBs play a complementary role by reducing the bond order of the N2 molecule, thereby promoting activation. The efficiency of N2 capture is directly linked to the electroaccepting characteristics of the LAs. A principal component analysis (PCA) reveals that the key factors influencing the electroaccepting power of LAs are the degree of pyramidalization and orbital occupation at the acidic site, as well as the local electrophilicity index. The LA-N2 interaction is found to be electrostatic with partially covalent character. Among the 21 LAs analyzed, triptycene-based systems exhibit the highest stability in forming LA-N2 complexes, highlighting their potential as effective N2-capturing agents. However, the N2 triple bond remains largely intact, necessitating the involvement of LBs in LA-N2-LB complexes for full activation, in a “push-pull” mechanism. Six LBs are analyzed in complexes with the most promising LAs. Bonding analysis indicates that the LB-N2 interaction can be regarded as a covalent bond, which may explain the main role of the LB in the reduction of the N2 bond order. Furthermore, the bond activation is significantly enhanced by increasing the nucleophilicity of the LB. Among all the LA-LB pair combinations, only three exhibit the defining characteristics of frustrated Lewis pairs (FLPs), with moderate interaction energies and substantial LA-LB distances. Our findings suggest that FLPs composed of triptycene-based LAs and tris-tert-butylphosphine represent the most promising candidates for N2 activation.
{"title":"Exploring N2 activation using novel Lewis acid/base pairs: computational insight into frustrated Lewis pair reactivity†","authors":"Xuban Gastearena, Jon Mattin Matxain, Fernando Ruipérez","doi":"10.1039/d4dt03425b","DOIUrl":"https://doi.org/10.1039/d4dt03425b","url":null,"abstract":"The activation of dinitrogen (N2) is a crucial step in synthesizing nitrogen-based compounds and remains a significant challenge due to its strong triple bond. Currently, industrial N2 conversion relies on the Haber-Bosch process, a highly energy-intensive method that utilizes transition metal-based catalysts. Frustrated Lewis pairs (FLPs) have emerged as a promising alternative for N2 activation without the need for transition metals. In this work, we employ density functional theory (DFT) to investigate the activation of N2 by transition metal-free Lewis acids (LAs) and bases (LBs). Our study demonstrates that LAs play a crucial role in capturing N2 and determining the thermodynamics of activation, while LBs play a complementary role by reducing the bond order of the N2 molecule, thereby promoting activation. The efficiency of N2 capture is directly linked to the electroaccepting characteristics of the LAs. A principal component analysis (PCA) reveals that the key factors influencing the electroaccepting power of LAs are the degree of pyramidalization and orbital occupation at the acidic site, as well as the local electrophilicity index. The LA-N2 interaction is found to be electrostatic with partially covalent character. Among the 21 LAs analyzed, triptycene-based systems exhibit the highest stability in forming LA-N2 complexes, highlighting their potential as effective N2-capturing agents. However, the N2 triple bond remains largely intact, necessitating the involvement of LBs in LA-N2-LB complexes for full activation, in a “push-pull” mechanism. Six LBs are analyzed in complexes with the most promising LAs. Bonding analysis indicates that the LB-N2 interaction can be regarded as a covalent bond, which may explain the main role of the LB in the reduction of the N2 bond order. Furthermore, the bond activation is significantly enhanced by increasing the nucleophilicity of the LB. Among all the LA-LB pair combinations, only three exhibit the defining characteristics of frustrated Lewis pairs (FLPs), with moderate interaction energies and substantial LA-LB distances. Our findings suggest that FLPs composed of triptycene-based LAs and tris-tert-butylphosphine represent the most promising candidates for N2 activation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"31 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258411","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 transport properties of polarons in a heterostructure are of great importance, since they can effectively affect the efficiency of photoelectric devices. However, the underlying mechanism of the polaron transfer rate and mode along intralayers or interlayers is still far from conclusive. Here, the stability and transport behaviors of polarons in polarized MoSSe few-layer structures were systematically investigated by constrained density functional theory (CDFT). It shows that the electron polarons in a MoSSe monolayer are more stable but have a smaller transfer rate than that of the hole polarons. Although the stability of the polarons will be slightly decreased by forming a parallel polarization heterostructure, the magnitude of the electron polaron transfer rate can be remarkably increased by 5 times and 71 times in their double- and three-layer case. In particular, it was unexpected to find that the original transfer mode along intralayer (in-plane) in monolayer can be completely overturned to along the interlayer (out-of-plane) by forming different stackings or increasing the MoSSe thickness. This unique behavior is strongly related to the polarization and the synergy effect of electronic coupling Hαβ and reorganization energy λ. Our findings offer a new perspective for the application of Janus MoSSe structures in optoelectronic devices and further advancement in the field of polarized low-dimensional materials.
{"title":"Tunable transport mode of polaron in polarized Janus MoSSe few-layer structures: a constrained density functional theory study","authors":"Hong-Shun He, Yun-Bo Li, Jifeng Luo, Qingxia Ge, Jian Wu, Daifeng Zou, Ying Xu, Wen-Jin Yin","doi":"10.1039/d4dt02909g","DOIUrl":"https://doi.org/10.1039/d4dt02909g","url":null,"abstract":"The transport properties of polarons in a heterostructure are of great importance, since they can effectively affect the efficiency of photoelectric devices. However, the underlying mechanism of the polaron transfer rate and mode along intralayers or interlayers is still far from conclusive. Here, the stability and transport behaviors of polarons in polarized MoSSe few-layer structures were systematically investigated by constrained density functional theory (CDFT). It shows that the electron polarons in a MoSSe monolayer are more stable but have a smaller transfer rate than that of the hole polarons. Although the stability of the polarons will be slightly decreased by forming a parallel polarization heterostructure, the magnitude of the electron polaron transfer rate can be remarkably increased by 5 times and 71 times in their double- and three-layer case. In particular, it was unexpected to find that the original transfer mode along intralayer (in-plane) in monolayer can be completely overturned to along the interlayer (out-of-plane) by forming different stackings or increasing the MoSSe thickness. This unique behavior is strongly related to the polarization and the synergy effect of electronic coupling <em>H</em><small><sub>αβ</sub></small> and reorganization energy <em>λ</em>. Our findings offer a new perspective for the application of Janus MoSSe structures in optoelectronic devices and further advancement in the field of polarized low-dimensional materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"47 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258412","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}
Rashida Yasmeen, Sheikh M. S. Islam, Jincheng Du, Mohammad Omary
Fluorous metal-organic frameworks, FMOFs, represent a superhydrophobic class of MOFs containing -CF3 or -F groups in their pores. The primary objective of this research is to computationally design functionalized FMOF-1 with X = -OCH3, -CN, -OH, -COOH and -NH2 instead of -CF3 and analyze their CO2 adsorption and separation characteristics. Grand Canonical Monte Carlo (GCMC) simulations are used to study adsorption properties of CO2, CH4 and N2 in all structures. Henry’s constant (KH) and isosteric heat of adsorption at infinite dilution (Qst0) estimated from GCMC simulations plus the binding energy (BE) from Mӧller-Plesset second-order perturbation theory (MP2) quantum-mechanical simulations characterize adsorbate-adsorbent interaction strengths. Such simulations predict a systematic enhancement of all KH, Qst0, and BE values in X-functionalized MOFs vs the parent FMOF-1. Among such functional MOFs, the X = -COOH structure is predicted to exhibit the largest CO2 uptake in the low-pressure region due to the strongest CO2/-COOH interaction strength, as supported by the largest KH (1.02 ×10-4 mol/kg/Pa). In contrast, at high pressures (30 bar), the X = -OH structure is predicted to exhibit the highest CO2 uptake. Indeed, replacing the -CF3 groups in FMOF-1 by any aforementioned X group is expected to afford higher CO2 uptake in the GCMC-simulated adsorption isotherms compared to the parent material. The selective adsorption of CO2 over CH4 and N2 was determined using the ideal adsorbed solution theory (IAST) method at 50:50 and 15:85 CO2/CH4 and CO2/N2 binary mixtures, respectively. The X = -COOH structure amounts to the largest selectivity (59.6 for CO2/CH4 and 128.7 in CO2/N2); i.e., nearly 40x and 43x higher vs FMOF-1 (1.5 and 3 in CO2/CH4 and CO2/N2, respectively) at 298 K and 0.1 bar. Functionalized MOFs for CO2 separation, natural gas purification, landfill gas separation, and/or CO2 flue gas capture suggest X = -OH, -COOH and -NH2 are promising to enhance adsorption capacity and selectivity.
{"title":"Versatile Functionalization of De-Fluorinated FMOF-1 Towards Enhanced Carbon Capture and Separation: A Predictive Molecular Simulation Study","authors":"Rashida Yasmeen, Sheikh M. S. Islam, Jincheng Du, Mohammad Omary","doi":"10.1039/d4dt03093a","DOIUrl":"https://doi.org/10.1039/d4dt03093a","url":null,"abstract":"Fluorous metal-organic frameworks, FMOFs, represent a superhydrophobic class of MOFs containing -CF3 or -F groups in their pores. The primary objective of this research is to computationally design functionalized FMOF-1 with X = -OCH3, -CN, -OH, -COOH and -NH2 instead of -CF3 and analyze their CO2 adsorption and separation characteristics. Grand Canonical Monte Carlo (GCMC) simulations are used to study adsorption properties of CO2, CH4 and N2 in all structures. Henry’s constant (KH) and isosteric heat of adsorption at infinite dilution (Qst0) estimated from GCMC simulations plus the binding energy (BE) from Mӧller-Plesset second-order perturbation theory (MP2) quantum-mechanical simulations characterize adsorbate-adsorbent interaction strengths. Such simulations predict a systematic enhancement of all KH, Qst0, and BE values in X-functionalized MOFs vs the parent FMOF-1. Among such functional MOFs, the X = -COOH structure is predicted to exhibit the largest CO2 uptake in the low-pressure region due to the strongest CO2/-COOH interaction strength, as supported by the largest KH (1.02 ×10-4 mol/kg/Pa). In contrast, at high pressures (30 bar), the X = -OH structure is predicted to exhibit the highest CO2 uptake. Indeed, replacing the -CF3 groups in FMOF-1 by any aforementioned X group is expected to afford higher CO2 uptake in the GCMC-simulated adsorption isotherms compared to the parent material. The selective adsorption of CO2 over CH4 and N2 was determined using the ideal adsorbed solution theory (IAST) method at 50:50 and 15:85 CO2/CH4 and CO2/N2 binary mixtures, respectively. The X = -COOH structure amounts to the largest selectivity (59.6 for CO2/CH4 and 128.7 in CO2/N2); i.e., nearly 40x and 43x higher vs FMOF-1 (1.5 and 3 in CO2/CH4 and CO2/N2, respectively) at 298 K and 0.1 bar. Functionalized MOFs for CO2 separation, natural gas purification, landfill gas separation, and/or CO2 flue gas capture suggest X = -OH, -COOH and -NH2 are promising to enhance adsorption capacity and selectivity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258413","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}
Jingjing Xu, Yan Xiao, Xiaowen Wu, Bingbing Zhang, Kui Wu
Combination of multiple anions (S2- and O2-) was developed as an effective method for exploring new excellent nonlinear optical (NLO) oxysulfides with adjustable property based on the flexible anion (S/O) ratio in structures. Note that mixed melilite-type oxysulfides with mixed alkaline-earth (Ae) and trivalent lanthanide (Ln) metals exhibit the natural noncentrosymmetric (NCS) and disordered structures that show the good NLO property. Herein, we introduced the low-coordination ZnS4 to replace with high-coordination AeS8 into La-based melilite to break the initial disordered structure for the born of a La2ZnGa2S6O NLO material with ordered-structure. Property investigation shows that La2ZnGa2S6O achieves a well-balanced NLO behavior between wide optical bandgap (3.0 eV) and ultra-strong phase-matching second harmonic generation (SHG) response (1.9 × AgGaS2). Among the melilite-type transition-metal oxysulfides, La2ZnGa2S6O exhibits the largest powder SHG response that can be attributed as the synergetic contributions of LaS7O, ZnS4 and GaS3O anionic groups based on the SHG-density analysis, which indicates that La2ZnGa2S6O is a potential NLO candidate for frequency-conversion application and combination of transition- and lanthanide-metals into structure provides a feasible way to design new large SHG oxysulfides.
{"title":"La2ZnGa2S6O: A Melilite-Type Transition Metal Oxysulfide achieving a Well-Balanced Nonlinear-Optical Behavior","authors":"Jingjing Xu, Yan Xiao, Xiaowen Wu, Bingbing Zhang, Kui Wu","doi":"10.1039/d4dt03569k","DOIUrl":"https://doi.org/10.1039/d4dt03569k","url":null,"abstract":"Combination of multiple anions (S2- and O2-) was developed as an effective method for exploring new excellent nonlinear optical (NLO) oxysulfides with adjustable property based on the flexible anion (S/O) ratio in structures. Note that mixed melilite-type oxysulfides with mixed alkaline-earth (Ae) and trivalent lanthanide (Ln) metals exhibit the natural noncentrosymmetric (NCS) and disordered structures that show the good NLO property. Herein, we introduced the low-coordination ZnS4 to replace with high-coordination AeS8 into La-based melilite to break the initial disordered structure for the born of a La2ZnGa2S6O NLO material with ordered-structure. Property investigation shows that La2ZnGa2S6O achieves a well-balanced NLO behavior between wide optical bandgap (3.0 eV) and ultra-strong phase-matching second harmonic generation (SHG) response (1.9 × AgGaS2). Among the melilite-type transition-metal oxysulfides, La2ZnGa2S6O exhibits the largest powder SHG response that can be attributed as the synergetic contributions of LaS7O, ZnS4 and GaS3O anionic groups based on the SHG-density analysis, which indicates that La2ZnGa2S6O is a potential NLO candidate for frequency-conversion application and combination of transition- and lanthanide-metals into structure provides a feasible way to design new large SHG oxysulfides.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258414","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 the utilisation of most oxide-based propane dehydrogenation (PDH) catalysts, each reaction–regeneration cycle necessitates both coke combustion and hydrogen reduction to achieve complete regeneration of the catalyst. However, the need for hydrogen reduction makes it difficult to use such catalysts in chemical looping oxidative dehydrogenation (CL-ODH) processes. This study prepared a series of CrZrOx catalysts with Cr/Zr atomic ratios ranging from 0.02 to 1 using a co-precipitation method. Electron paramagnetic resonance (EPR) analysis revealed that the catalyst surface in its oxidised state is rich in oxygen vacancies. These vacancies created numerous coordinated unsaturated Zr (Zrcus)-based active sites directly linked to the catalyst's unique catalytic activity. This catalyst was paired with a Cu2MnOx@Na2WO4 oxygen carrier to perform the CL-ODH of propane. The results demonstrated that the catalyst–oxygen carrier coupling system significantly enhanced single-pass propane conversion in the PDH process, increasing the initial propane conversion from 27.2% to 35.9%. The enhanced conversion, along with the observed hydrogen consumption over time, confirmed that the PDH process was coupled with hydrogen oxidation via the lattice oxygen of the oxygen carrier. This coupling broke through the thermodynamic equilibrium, thereby significantly improving the single-pass propane conversion. These findings provide valuable insights for designing novel catalyst systems tailored for the CL-ODH of propane.
{"title":"Design of a CrZrOx–Cu2MnOx@Na2WO4 catalyst–oxygen carrier system for efficient chemical looping oxidative dehydrogenation of propane","authors":"Ziyang Liu, Peng Bai, Benjing Xu, Pingping Wu, Hao Wu, Haoran Sun, Junji Li, Zifeng Yan","doi":"10.1039/d4dt03391d","DOIUrl":"https://doi.org/10.1039/d4dt03391d","url":null,"abstract":"In the utilisation of most oxide-based propane dehydrogenation (PDH) catalysts, each reaction–regeneration cycle necessitates both coke combustion and hydrogen reduction to achieve complete regeneration of the catalyst. However, the need for hydrogen reduction makes it difficult to use such catalysts in chemical looping oxidative dehydrogenation (CL-ODH) processes. This study prepared a series of CrZrO<small><sub><em>x</em></sub></small> catalysts with Cr/Zr atomic ratios ranging from 0.02 to 1 using a co-precipitation method. Electron paramagnetic resonance (EPR) analysis revealed that the catalyst surface in its oxidised state is rich in oxygen vacancies. These vacancies created numerous coordinated unsaturated Zr (Zr<small><sub>cus</sub></small>)-based active sites directly linked to the catalyst's unique catalytic activity. This catalyst was paired with a Cu<small><sub>2</sub></small>MnO<small><sub><em>x</em></sub></small>@Na<small><sub>2</sub></small>WO<small><sub>4</sub></small> oxygen carrier to perform the CL-ODH of propane. The results demonstrated that the catalyst–oxygen carrier coupling system significantly enhanced single-pass propane conversion in the PDH process, increasing the initial propane conversion from 27.2% to 35.9%. The enhanced conversion, along with the observed hydrogen consumption over time, confirmed that the PDH process was coupled with hydrogen oxidation <em>via</em> the lattice oxygen of the oxygen carrier. This coupling broke through the thermodynamic equilibrium, thereby significantly improving the single-pass propane conversion. These findings provide valuable insights for designing novel catalyst systems tailored for the CL-ODH of propane.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"15 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192618","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}
Andrey P. Kroitor, Alexander G. Martynov, Yulia G. Gorbunova, Aslan Yu Tsivadze, Alexander B. Sorokin
The novel ruthenium octa-n-butoxy-naphthalocyanine complex was shown to retain essentially monomeric state in diluted solutions. It was succesfully applied as homogeneous catalyst for the carbene insertion to N-H bonds of amines with various substitution pattern providing high yields of glycine derivatives.
{"title":"Non-aggregated ruthenium naphthalocyanine enabling homogeneous carbene insertion into N-H bonds at low catalyst loading","authors":"Andrey P. Kroitor, Alexander G. Martynov, Yulia G. Gorbunova, Aslan Yu Tsivadze, Alexander B. Sorokin","doi":"10.1039/d4dt03263b","DOIUrl":"https://doi.org/10.1039/d4dt03263b","url":null,"abstract":"The novel ruthenium octa-n-butoxy-naphthalocyanine complex was shown to retain essentially monomeric state in diluted solutions. It was succesfully applied as homogeneous catalyst for the carbene insertion to N-H bonds of amines with various substitution pattern providing high yields of glycine derivatives.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"93 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192600","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}
Darya Chaplygina, Olga V. Patrusheva, Congcong Chen, Anna V. Shtareva, Constantinos C. Stoumpos, Ruslan Kevorkyants, Alexei Emeline, Dmitry Shtarev
This work reports on the synthesis, crystal structure, morphology, and optoelectronic properties of novel quasi low-dimensional hybrid (bromomethyl)pyridinium crystalline phases (2-BrCH2PyH)Pb2Br5, (3-BrCH2PyH)PbBr3, and (4-BrCH2PyH)PbBr3. The first compound forms quasi 2D crystals, while other two species crystallize as quasi 1D structures. DFT calculations predict that the bromides are semiconductors featuring electronic VB to CB transitions of ~3.2 eV. (2-BrCH2PyH)Pb2Br5 and (3-BrCH2PyH)PbBr3 exhibit low-temperature (77 K) photoluminescence (PL). PL is not observed in (4-BrCH2PyH)PbBr3 that is presumably due to a small distance between the lead cations and bromine atoms of the 4-BrCH2PyH cations facilitating radiationless electronic transition. The studied species demonstrate quantum size effects.
{"title":"The effect of ring substituent position on the structural and optoelectronic properties of novel quasi low-dimensional hybrid 2-, 3-, and 4-(bromomethyl)pyridinium lead bromides","authors":"Darya Chaplygina, Olga V. Patrusheva, Congcong Chen, Anna V. Shtareva, Constantinos C. Stoumpos, Ruslan Kevorkyants, Alexei Emeline, Dmitry Shtarev","doi":"10.1039/d4dt02158d","DOIUrl":"https://doi.org/10.1039/d4dt02158d","url":null,"abstract":"This work reports on the synthesis, crystal structure, morphology, and optoelectronic properties of novel quasi low-dimensional hybrid (bromomethyl)pyridinium crystalline phases (2-BrCH2PyH)Pb2Br5, (3-BrCH2PyH)PbBr3, and (4-BrCH2PyH)PbBr3. The first compound forms quasi 2D crystals, while other two species crystallize as quasi 1D structures. DFT calculations predict that the bromides are semiconductors featuring electronic VB to CB transitions of ~3.2 eV. (2-BrCH2PyH)Pb2Br5 and (3-BrCH2PyH)PbBr3 exhibit low-temperature (77 K) photoluminescence (PL). PL is not observed in (4-BrCH2PyH)PbBr3 that is presumably due to a small distance between the lead cations and bromine atoms of the 4-BrCH2PyH cations facilitating radiationless electronic transition. The studied species demonstrate quantum size effects.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"50 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192601","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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