The pseudo-binary phases in the In2Se3-Ga2Se3 system have drawn attention due to their interesting structural features and exciting non-linear optical (NLO) properties. Although the phases have been known since 1977, a detailed structural characterization has not been investigated in previous studies. In this research program, the pseudo-binary In2-xGaxSe3 (x = 0.6-1.4) (hexagonal, P65/P61) has been prepared using high-temperature synthesis and characterized using X-ray diffraction techniques and DFT calculations. For x ≤ 1, the structure is similar to parent γ-In2Se3 and adopts the layered defect wurtzite type (γ1), where gallium preferentially substitutes the tetrahedrally coordinated indium site without affecting the indium at the trigonal bipyramidal (TBP) environment. At x = 1, the ordered γ1 -GaInSe3 is formed. In the compositional range 1.2 < x ≤ 1.4, an ideal defect wurtzite structure (γ2) is observed, and herein, both cationic sites are tetrahedrally coordinated by selenium. Ga occupies one of the two tetrahedrally coordinated cationic sites in this region, while the other site is statistically mixed between Ga and In. Interestingly, x=1.2 the structure is heavily disordered and can be interpreted in terms of an incoherent intergrowth of γ1-and γ2-phases. A detailed theoretical calculation is employed on various compounds in the III2-VI3 family (e.g. α-Al2S3, α-Ga2S3, and γ-In2Se3, and InGaSe3) to unveil the preference of Ga for tetrahedral co-ordination in the pseudo-binary In2-xGaxSe3.
In2Se3-Ga2Se3 系统中的伪二元相因其有趣的结构特征和令人兴奋的非线性光学（NLO）特性而备受关注。虽然人们早在 1977 年就知道了这些相，但在以前的研究中还没有对它们的详细结构特征进行过调查。在本研究计划中，采用高温合成法制备了伪二元 In2-xGaxSe3（x = 0.6-1.4）（六边形，P65/P61），并利用 X 射线衍射技术和 DFT 计算对其进行了表征。当 x ≤ 1 时，其结构与母体 γ-In2Se3 相似，采用层状缺陷乌兹石类型（γ1），其中镓优先取代了四面体配位的铟位，而不影响三方双锥（TBP）环境中的铟。在 x = 1 时，形成了有序的 γ1 -GaInSe3。在 1.2 < x ≤ 1.4 的成分范围内，观察到一种理想的有缺陷乌兹特结构 (γ2)，其中，两个阳离子位均由硒四面体配位。镓占据了该区域两个四面体配位阳离子位点中的一个，而另一个位点则由镓和铟统计混合而成。有趣的是，当 x=1.2 时，结构严重无序，可以解释为 γ1 和 γ2 相的不连贯互生。我们对 III2-VI3 家族的各种化合物（如 α-Al2S3、α-Ga2S3、γ-In2Se3 和 InGaSe3）进行了详细的理论计算，揭示了在伪二元 In2-xGaxSe3 中 Ga 对四面体配位的偏好。
{"title":"Unveiling the Unique Site Preference of Ga in the Defect Wurtzite Type In2Se3-Ga2Se3 System: An Experimental and Computational Study","authors":"Siddha Sankalpa Sethi, Achintya Lakshan, Ahin Roy, Siddhartha Das, Karabi Das, Partha Pratim Jana","doi":"10.1039/d5dt00231a","DOIUrl":"https://doi.org/10.1039/d5dt00231a","url":null,"abstract":"The pseudo-binary phases in the In2Se3-Ga2Se3 system have drawn attention due to their interesting structural features and exciting non-linear optical (NLO) properties. Although the phases have been known since 1977, a detailed structural characterization has not been investigated in previous studies. In this research program, the pseudo-binary In2-xGaxSe3 (x = 0.6-1.4) (hexagonal, P65/P61) has been prepared using high-temperature synthesis and characterized using X-ray diffraction techniques and DFT calculations. For x ≤ 1, the structure is similar to parent γ-In2Se3 and adopts the layered defect wurtzite type (γ1), where gallium preferentially substitutes the tetrahedrally coordinated indium site without affecting the indium at the trigonal bipyramidal (TBP) environment. At x = 1, the ordered γ1 -GaInSe3 is formed. In the compositional range 1.2 < x ≤ 1.4, an ideal defect wurtzite structure (γ2) is observed, and herein, both cationic sites are tetrahedrally coordinated by selenium. Ga occupies one of the two tetrahedrally coordinated cationic sites in this region, while the other site is statistically mixed between Ga and In. Interestingly, x=1.2 the structure is heavily disordered and can be interpreted in terms of an incoherent intergrowth of γ1-and γ2-phases. A detailed theoretical calculation is employed on various compounds in the III2-VI3 family (e.g. α-Al2S3, α-Ga2S3, and γ-In2Se3, and InGaSe3) to unveil the preference of Ga for tetrahedral co-ordination in the pseudo-binary In2-xGaxSe3.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847045","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}
Gulaim A. Seisenbaeva, Lars kloo, Peter Agback, Vadim G Kessler
Polymerization isomerism is potentially important for metal alkoxides as precursors of oxide materials. Here, we present this phenomenon for tungsten oxo-methoxide reporting the molecular and crystal structure of its polymeric form [WO(OMe)4]∞(1) along with its dimeric form W2O2(OMe)8(2), and one to higher extent oxo-substituted by-product of the synthesis, Li2(MeOH)6W12O29(OMe)16(3).
{"title":"Polymerisation Isomerism of Tungsten(VI) Oxomethoxide: New Insights into Structure and Reactivity of Non-Cluster Metal Oxoalkoxide Aggregates","authors":"Gulaim A. Seisenbaeva, Lars kloo, Peter Agback, Vadim G Kessler","doi":"10.1039/d5dt00348b","DOIUrl":"https://doi.org/10.1039/d5dt00348b","url":null,"abstract":"Polymerization isomerism is potentially important for metal alkoxides as precursors of oxide materials. Here, we present this phenomenon for tungsten oxo-methoxide reporting the molecular and crystal structure of its polymeric form [WO(OMe)4]∞(1) along with its dimeric form W2O2(OMe)8(2), and one to higher extent oxo-substituted by-product of the synthesis, Li2(MeOH)6W12O29(OMe)16(3).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"130 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847040","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}
Karen Valencia G., Agileo Hernández-Gordillo, Lorena Cerezo Duran, Sandra Elizabeth Rodil
This study introduced advanced photocatalytic heterojunctions by integrating CdS nanofibers with defect-rich polymeric carbon nitride (g-C₃N₄-V₀). Two g-C₃N₄-V₀ variants (CN1 and CN2) with varying nitrogen vacancy concentrations were synthesized, enhancing visible and near-infrared light absorption. Eight heterojunctions with different CN1 and CN2 contents (5–20 wt%) were prepared and tested for hydrogen evolution reaction (HER) in ethanol-water solutions without a Pt co-catalyst. Under optimized conditions (photocatalyst mass: 0.0125 g/L, light intensity: 10 mW/cm²), the CS/CN1-15 and CS/CN2-10 heterojunctions achieved HER rates of 4.43 and 5.25 mmolh⁻¹g⁻¹, respectively—doubling the efficiency of comparable systems. Their superior performance was attributed to enhanced light absorption, efficient charge separation, and reduced charge transfer resistance. The CS/CN2-10 heterojunction also demonstrated long-term stability and reduced photocorrosion, emphasizing its promise for sustainable hydrogen production.
{"title":"Blue-Light Hydrogen Production via CdS/g-C₃N₄ Heterojunctions","authors":"Karen Valencia G., Agileo Hernández-Gordillo, Lorena Cerezo Duran, Sandra Elizabeth Rodil","doi":"10.1039/d5dt00187k","DOIUrl":"https://doi.org/10.1039/d5dt00187k","url":null,"abstract":"This study introduced advanced photocatalytic heterojunctions by integrating CdS nanofibers with defect-rich polymeric carbon nitride (g-C₃N₄-V₀). Two g-C₃N₄-V₀ variants (CN1 and CN2) with varying nitrogen vacancy concentrations were synthesized, enhancing visible and near-infrared light absorption. Eight heterojunctions with different CN1 and CN2 contents (5–20 wt%) were prepared and tested for hydrogen evolution reaction (HER) in ethanol-water solutions without a Pt co-catalyst. Under optimized conditions (photocatalyst mass: 0.0125 g/L, light intensity: 10 mW/cm²), the CS/CN1-15 and CS/CN2-10 heterojunctions achieved HER rates of 4.43 and 5.25 mmolh⁻¹g⁻¹, respectively—doubling the efficiency of comparable systems. Their superior performance was attributed to enhanced light absorption, efficient charge separation, and reduced charge transfer resistance. The CS/CN2-10 heterojunction also demonstrated long-term stability and reduced photocorrosion, emphasizing its promise for sustainable hydrogen production.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"75 2 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841528","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 reaction of an ambiphilic 1,4,2-diazaborole with C=O and C=S bonds results in formal (3+2) cycloaddition and has allowed the synthesis of a family of 1,3,2-oxazaborole and 1,3,2-thiazaborole derivatives. Computational calculations have indicated a dipolar mechanism where the π bond is concertedly activated via the Lewis acidic boron centre and the nucleophilic C5 position of the 1,4,2-diazaborole. In the case of methylisothiocyanate, preference for C=S over C=N addition is observed, and has been rationalized according to mechanistic calculations. A spirocyclic bis(1,3,2-thiazaborole) has been observed from the double activation of CS2.
{"title":"C=O and C=S bond activation by an annulated 1,4,2-diazaborole","authors":"Vignesh Pattathil, Conor Pranckevicius","doi":"10.1039/d5dt00642b","DOIUrl":"https://doi.org/10.1039/d5dt00642b","url":null,"abstract":"The reaction of an ambiphilic 1,4,2-diazaborole with C=O and C=S bonds results in formal (3+2) cycloaddition and has allowed the synthesis of a family of 1,3,2-oxazaborole and 1,3,2-thiazaborole derivatives. Computational calculations have indicated a dipolar mechanism where the π bond is concertedly activated via the Lewis acidic boron centre and the nucleophilic C5 position of the 1,4,2-diazaborole. In the case of methylisothiocyanate, preference for C=S over C=N addition is observed, and has been rationalized according to mechanistic calculations. A spirocyclic bis(1,3,2-thiazaborole) has been observed from the double activation of CS<small><sub>2</sub></small>.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"108 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841529","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}
Vijay Parmar, Gemma Kate Gransbury, Sophie C. Corner, Wei-Hao Chou, Stephen Hill, Richard E. P. Winpenny, Nicholas F Chilton, David P Mills
Two heteroleptic octahedral Dy(III) cis-aryloxidecomplexes, [Dy(OPh*)2(THF)3X] {HOPh* = 2,6-bis(diphenyl-methyl)-4-tert-butylphenol; X = Cl (1), Br (2)}, have been characterised by multi-frequency electron paramagnetic resonance (EPR) spectroscopy to determine gz = 18.9(1) for 1 and 18.3(6) for 2. These are rare examples of Dy(III) single-molecule magnets that have observable EPR spectra.
{"title":"Direct characterisation of mJ = ± 15/2 ground state in octahedral Dy(III) single-molecule magnets","authors":"Vijay Parmar, Gemma Kate Gransbury, Sophie C. Corner, Wei-Hao Chou, Stephen Hill, Richard E. P. Winpenny, Nicholas F Chilton, David P Mills","doi":"10.1039/d5dt00862j","DOIUrl":"https://doi.org/10.1039/d5dt00862j","url":null,"abstract":"Two heteroleptic octahedral Dy(III) cis-aryloxidecomplexes, [Dy(OPh*)2(THF)3X] {HOPh* = 2,6-bis(diphenyl-methyl)-4-tert-butylphenol; X = Cl (1), Br (2)}, have been characterised by multi-frequency electron paramagnetic resonance (EPR) spectroscopy to determine gz = 18.9(1) for 1 and 18.3(6) for 2. These are rare examples of Dy(III) single-molecule magnets that have observable EPR spectra.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"22 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841525","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}
White light-emitting materials (WLEMs) offer significant advantages over traditional incandescent light bulbs and compact fluorescent lamps due to their ability to provide pure white-light emission, low energy consumption, and suitability for large-area thin-film fabrication. White light can be obtained by several types of materials involving lanthanide ions and their combinations, but single component emitters based on lathanide coordination assemblies remain rare and desirable towards thinner devices that are, therefore, easier to control and that require fewer manufacturing steps. Over the past decade, single-component lanthanide coordination assemblies have garnered considerable attention as white-light-emitting photoluminescent materials, leading to notable advancements. The current review gives an overview of recent progress in this field, emphasizing the WLEMs and photoluminescent colour-tuning properties realized in the single-component lanthanide coordination assemblies (Sm3+ or Eu3+ or Dy3+) which covers the origin, generation, and manipulation of different types of photoluminescence derived from ligand-centered fluorescence in the blue range and metal centered emissions in the visible region.
{"title":"Single-component white-light-emitting materials based on lanthanide coordination assemblies","authors":"M. L. P. Reddy, BEJOY MOHAN DAS K S","doi":"10.1039/d5dt00172b","DOIUrl":"https://doi.org/10.1039/d5dt00172b","url":null,"abstract":"White light-emitting materials (WLEMs) offer significant advantages over traditional incandescent light bulbs and compact fluorescent lamps due to their ability to provide pure white-light emission, low energy consumption, and suitability for large-area thin-film fabrication. White light can be obtained by several types of materials involving lanthanide ions and their combinations, but single component emitters based on lathanide coordination assemblies remain rare and desirable towards thinner devices that are, therefore, easier to control and that require fewer manufacturing steps. Over the past decade, single-component lanthanide coordination assemblies have garnered considerable attention as white-light-emitting photoluminescent materials, leading to notable advancements. The current review gives an overview of recent progress in this field, emphasizing the WLEMs and photoluminescent colour-tuning properties realized in the single-component lanthanide coordination assemblies (Sm3+ or Eu3+ or Dy3+) which covers the origin, generation, and manipulation of different types of photoluminescence derived from ligand-centered fluorescence in the blue range and metal centered emissions in the visible region.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"38 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report the variation in zero-point energies, ΔE0HL and their distribution, investigated through changes in thermal spin relaxation behavior and cooperativity, in the 3D Hofmann-type guest-free, different-sized nanocrystalline spin-crossover coordination networks, {Fe1−xMx(pz)[Pd(CN)4]}, 0 ≤ x ≤1, where M(II) = Zn(II), Co(II), and Ni(II). Additionally, we synthesize the [Fe(pz)Pd(CN)4] nanocrystals embedded in different polymeric matrices, including Poly(methyl methacrylate) (PMMA), Polyethylene glycol 6000 (PEG-6000), and Polyvinylpyrrolidone K-30 (PVP K-30). The resulting nanostructures are phase-pure, well-crystallized and exhibit a tetragonal phase. High-resolution transmission electron microscopy (HRTEM) confirms that the nanostructures are nearly square-shaped, with well-defined sizes. The abrupt, incomplete, and gradual nature of the thermal spin relaxation behavior observed from the magnetic data for pure, doped, and polymer-embedded nanocrystals is collectively explained by the local and long-range fluctuations in the crystal fields experienced by the Fe(II) spin-crossover centers, variation in nucleation barrier energy influencing elastic properties, kinetic effects linked to modification in nucleation preferential sites during spin-state switching, as well as chemical pressure, lattice-strains and imperfections, thus altering the in-plane and out-of-plane interactions that influence the cooperativity variation and are responsible for the relative stabilization of the high-spin or low-spin states by modifying the ΔE0HL. A 3D mechanoelastic model is employed to interpret the observed magnetic behavior of pure, doped, and polymer-embedded nanocrystals, offering deeper insights into the underlying mechanisms governing spin-state transitions at the nanoscale.
{"title":"Tailoring Zero-Point Energies in Nanocrystalline 3D Hofmann-Type Spin-Crossover Networks {Fe1−xMx(pz)[Pd(CN)4]}: Impact of Size, Composition, and Surrounding Matrices","authors":"Pradip Chakraborty, Chinmoy Das, Ajana Dutta, Denisa Coltuneac, Laurentiu Stoleriu","doi":"10.1039/d5dt00565e","DOIUrl":"https://doi.org/10.1039/d5dt00565e","url":null,"abstract":"We report the variation in zero-point energies, ΔE0HL and their distribution, investigated through changes in thermal spin relaxation behavior and cooperativity, in the 3D Hofmann-type guest-free, different-sized nanocrystalline spin-crossover coordination networks, {Fe1−xMx(pz)[Pd(CN)4]}, 0 ≤ x ≤1, where M(II) = Zn(II), Co(II), and Ni(II). Additionally, we synthesize the [Fe(pz)Pd(CN)4] nanocrystals embedded in different polymeric matrices, including Poly(methyl methacrylate) (PMMA), Polyethylene glycol 6000 (PEG-6000), and Polyvinylpyrrolidone K-30 (PVP K-30). The resulting nanostructures are phase-pure, well-crystallized and exhibit a tetragonal phase. High-resolution transmission electron microscopy (HRTEM) confirms that the nanostructures are nearly square-shaped, with well-defined sizes. The abrupt, incomplete, and gradual nature of the thermal spin relaxation behavior observed from the magnetic data for pure, doped, and polymer-embedded nanocrystals is collectively explained by the local and long-range fluctuations in the crystal fields experienced by the Fe(II) spin-crossover centers, variation in nucleation barrier energy influencing elastic properties, kinetic effects linked to modification in nucleation preferential sites during spin-state switching, as well as chemical pressure, lattice-strains and imperfections, thus altering the in-plane and out-of-plane interactions that influence the cooperativity variation and are responsible for the relative stabilization of the high-spin or low-spin states by modifying the ΔE0HL. A 3D mechanoelastic model is employed to interpret the observed magnetic behavior of pure, doped, and polymer-embedded nanocrystals, offering deeper insights into the underlying mechanisms governing spin-state transitions at the nanoscale.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"6 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841532","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 stability issue induced by surface defects of perovskite films remains one of the key constraints in facilitating the commercial adoption of perovskite solar cells (PSCs). Developing reliable passivation strategies based on inexpensive multifunctional passivation materials is expected to solve the problems above. Here, gelatin-derived carbon nanosheets (G-DC) prepared by the self-doping template method are developed to strengthen the surface of perovskite films, thus enhancing the heat resistance of PSCs. This two-dimensional passivation material has an ultra-thin layered structure and contains abundant heteroatoms such as N and O, which can effectively reduce surface defects and relieve the impact of residual lead iodide in perovskite films. The excellent interface compatibility of G-DC promotes more efficient carrier extraction at the rear interface of PSCs, greatly reducing non-radiative recombination. Thanks to these, the optimal device with G-DC modification has a power conversion efficiency of up to 21.65%, which is higher than the control device of 20.32%. Furthermore, thermally induced organic component loss and ion migration of the modified PSCs are significantly suppressed due to the interactions between G-DC and perovskite. Finally, the G-DC modified devices maintain 87% of the initial efficiency after aging in an inert atmosphere at 85 ℃ for 720 h.
{"title":"Surface reinforcement of perovskite films with heteroatom-modulated carbon nanosheets for heat-resistant solar cells","authors":"Lele Qiu, Wanyu Tian, Ming Xu, Jian Xiao, Jing Liang, Fang-Jing Liu, Yunpeng Zhao","doi":"10.1039/d5dt00652j","DOIUrl":"https://doi.org/10.1039/d5dt00652j","url":null,"abstract":"The stability issue induced by surface defects of perovskite films remains one of the key constraints in facilitating the commercial adoption of perovskite solar cells (PSCs). Developing reliable passivation strategies based on inexpensive multifunctional passivation materials is expected to solve the problems above. Here, gelatin-derived carbon nanosheets (G-DC) prepared by the self-doping template method are developed to strengthen the surface of perovskite films, thus enhancing the heat resistance of PSCs. This two-dimensional passivation material has an ultra-thin layered structure and contains abundant heteroatoms such as N and O, which can effectively reduce surface defects and relieve the impact of residual lead iodide in perovskite films. The excellent interface compatibility of G-DC promotes more efficient carrier extraction at the rear interface of PSCs, greatly reducing non-radiative recombination. Thanks to these, the optimal device with G-DC modification has a power conversion efficiency of up to 21.65%, which is higher than the control device of 20.32%. Furthermore, thermally induced organic component loss and ion migration of the modified PSCs are significantly suppressed due to the interactions between G-DC and perovskite. Finally, the G-DC modified devices maintain 87% of the initial efficiency after aging in an inert atmosphere at 85 ℃ for 720 h.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"58 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841531","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}
Damien Culver, Marco Mais, Min-Chul Kang, Lin Zhou, Frédéric Perras
Single atom, low valent transition metals are important for heterogeneous catalysis but are challenging to generate and stabilize in a well-defined manner. Herein, we explored the functionalization of silica with well-defined N-heterocyclic phosphenium (NHP) ions to heterogenize low-valent metals. The surface electro-statically bound [NHP]+ coordinate to Pt(0) precursors resulting in well-defined, chemisorbed [(NHP)Pt(0)Ln]+ sites. The resulting materials catalyze the hydrosilylation of alkynes and exhibit activities and selectivities that rival the current industry standard homogeneous catalysts. The catalysts leach Pt limiting their recyclability; however, recycling studies support that the high regioselectivities arise from heterogeneous sites and Pt particles do not form on the surface. We suspect that this phosphenium-based immobilization strategy will result in stable, tunable, low valent heterogeneous transition metal catalysts in a wider array of catalytic reactions.
{"title":"Well-defined Pt(0) heterogeneous hydrosilylation catalysts supported by a surface bound phosphenium","authors":"Damien Culver, Marco Mais, Min-Chul Kang, Lin Zhou, Frédéric Perras","doi":"10.1039/d5dt00680e","DOIUrl":"https://doi.org/10.1039/d5dt00680e","url":null,"abstract":"Single atom, low valent transition metals are important for heterogeneous catalysis but are challenging to generate and stabilize in a well-defined manner. Herein, we explored the functionalization of silica with well-defined N-heterocyclic phosphenium (NHP) ions to heterogenize low-valent metals. The surface electro-statically bound [NHP]<small><sup>+</sup></small> coordinate to Pt(0) precursors resulting in well-defined, chemisorbed [(NHP)Pt(0)L<small><sub>n</sub></small>]<small><sup>+</sup></small> sites. The resulting materials catalyze the hydrosilylation of alkynes and exhibit activities and selectivities that rival the current industry standard homogeneous catalysts. The catalysts leach Pt limiting their recyclability; however, recycling studies support that the high regioselectivities arise from heterogeneous sites and Pt particles do not form on the surface. We suspect that this phosphenium-based immobilization strategy will result in stable, tunable, low valent heterogeneous transition metal catalysts in a wider array of catalytic reactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"117 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841533","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 crucial role of lone pair of electrons in the functionality of materials has been unprecedented. The present study reports a prolific correlation between the local structure and the stereochemical activity of the lone pairs of Bi3+ ions in the sillenite structure. The structural changes induced by variations in annealing temperatures greatly influenced the stereochemical activity of Bi3+ ion lone pairs, which, in turn, dictated the capacity for the incorporation of probing lanthanide ions in its proximity. Increased annealing temperature induces a transformation of Bi12GaO20±δ samples from a nanoscale to a bulk length scale. During the nano-to-bulk conversion of sillenite-structured Bi12GaO20±δ, the emergence of long-range ordering synchronized with the enhanced stereochemical activity of the lone pair, and this amelioration in activity led to the attrition of luminescent lanthanide ions (Eu3+, Tb3+, Er3+, and Yb3+) from the sillenite phase. Based on detailed experimental and theoretical investigations, it was envisioned that while finite size impeded the long-range translational repeatability of lone pairs in the nano-crystalline Bi12GaO20±δ sample, the concurrent existence of random geometrical distortion induces averaging of interactions at the focal Bi-site, suppressing the stereochemical activity. In high-temperature annealed bulk Bi12GaO20±δ sillenite samples, the long-range symmetrical arrangement of Bi3+ lone pairs balances the repulsive interactions. To maintain this balance, guest (doped) lanthanide ions were eliminated from the host lattice, resulting in phase separation. It is believed that the observations and rationalizations established between the local structure and the stereochemical activity of Bi3+ ion lone pair will aid in designing future bismuth-based functional materials.
{"title":"Lone pair electron-induced attrition of lanthanide ions from a sillenite-structured bismuth gallate host","authors":"Nistha Singh, Sandeep Nigam, Chiranjib Majumder, Nidhi Gupta, Vasanthakumaran Sudarsan","doi":"10.1039/d4dt03483j","DOIUrl":"https://doi.org/10.1039/d4dt03483j","url":null,"abstract":"The crucial role of lone pair of electrons in the functionality of materials has been unprecedented. The present study reports a prolific correlation between the local structure and the stereochemical activity of the lone pairs of Bi<small><sup>3+</sup></small> ions in the sillenite structure. The structural changes induced by variations in annealing temperatures greatly influenced the stereochemical activity of Bi<small><sup>3+</sup></small> ion lone pairs, which, in turn, dictated the capacity for the incorporation of probing lanthanide ions in its proximity. Increased annealing temperature induces a transformation of Bi<small><sub>12</sub></small>GaO<small><sub>20±<em>δ</em></sub></small> samples from a nanoscale to a bulk length scale. During the nano-to-bulk conversion of sillenite-structured Bi<small><sub>12</sub></small>GaO<small><sub>20±<em>δ</em></sub></small>, the emergence of long-range ordering synchronized with the enhanced stereochemical activity of the lone pair, and this amelioration in activity led to the attrition of luminescent lanthanide ions (Eu<small><sup>3+</sup></small>, Tb<small><sup>3+</sup></small>, Er<small><sup>3+</sup></small>, and Yb<small><sup>3+</sup></small>) from the sillenite phase. Based on detailed experimental and theoretical investigations, it was envisioned that while finite size impeded the long-range translational repeatability of lone pairs in the nano-crystalline Bi<small><sub>12</sub></small>GaO<small><sub>20±<em>δ</em></sub></small> sample, the concurrent existence of random geometrical distortion induces averaging of interactions at the focal Bi-site, suppressing the stereochemical activity. In high-temperature annealed bulk Bi<small><sub>12</sub></small>GaO<small><sub>20±<em>δ</em></sub></small> sillenite samples, the long-range symmetrical arrangement of Bi<small><sup>3+</sup></small> lone pairs balances the repulsive interactions. To maintain this balance, guest (doped) lanthanide ions were eliminated from the host lattice, resulting in phase separation. It is believed that the observations and rationalizations established between the local structure and the stereochemical activity of Bi<small><sup>3+</sup></small> ion lone pair will aid in designing future bismuth-based functional materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837386","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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