Interest for the development of various innovative synthesis approaches for producing biomimetic nanoparticles (NPs) arises from their remarkable ability to achieve effective cellular uptake for various biomedical applications. In this study, citrate, one of the main organic constituent in natural bones, serves as an efficient post-synthesis surface modifier for Eu(III) doped hydroxyapatite nanoparticles (Eu:HAp NPs) enabling effective functionalization of the as-synthesized material. The as-prepared (both bared and citrate modified) Eu:HAp NPs are characterized by various analytical techniques like XRD, FTIR, FESEM, TEM, DLS, etc. Characterization studies indicated that this synthesis method alters only the surface characteristic properties, while the core structural properties of particles remains unaffected. FTIR and DLS-zeta potential studies reveal citrate modification occurs on the NPs surface via chemisorptions, inducing negatively charged carboxylate (COO-) sites and improving colloidal stability. Interestingly, citrate modification does not affect the photoluminescent emission characteristics of as-prepared NPs. Additionally, biocompatibility and cell imaging properties are analyzed to evaluate the effect of citrate modification of NPs on cellular uptake capacity. Both bared and citrate modified Eu:HAp NPs do not show any significant toxicity in HEK-293 and MDA-MB-231 cell lines. Also, cells treated with citrate modified Eu:HAp NPs exhibits more red-color luminescence in confocal images and enhanced cellular uptake in FACS analysis compared to bared Eu:HAp NPs treatment. Therefore, due to their excellent biocompatibility and cellular uptake, the synthesized NPs are best suited for bioimaging applications. Further, this approach can also be applied for surface modification with various targeting ligands for diverse use.
{"title":"Post-synthetic citrate modification of Eu(III) doped hydroxyapatite nanoparticles for enhanced cellular uptake in bioimaging applications","authors":"Thoudam Chanchan Devi, Pritam Das, Souma Ghosh, Rajkumar Banerjee, David Thiyam","doi":"10.1039/d5dt02785c","DOIUrl":"https://doi.org/10.1039/d5dt02785c","url":null,"abstract":"Interest for the development of various innovative synthesis approaches for producing biomimetic nanoparticles (NPs) arises from their remarkable ability to achieve effective cellular uptake for various biomedical applications. In this study, citrate, one of the main organic constituent in natural bones, serves as an efficient post-synthesis surface modifier for Eu(III) doped hydroxyapatite nanoparticles (Eu:HAp NPs) enabling effective functionalization of the as-synthesized material. The as-prepared (both bared and citrate modified) Eu:HAp NPs are characterized by various analytical techniques like XRD, FTIR, FESEM, TEM, DLS, etc. Characterization studies indicated that this synthesis method alters only the surface characteristic properties, while the core structural properties of particles remains unaffected. FTIR and DLS-zeta potential studies reveal citrate modification occurs on the NPs surface via chemisorptions, inducing negatively charged carboxylate (COO-) sites and improving colloidal stability. Interestingly, citrate modification does not affect the photoluminescent emission characteristics of as-prepared NPs. Additionally, biocompatibility and cell imaging properties are analyzed to evaluate the effect of citrate modification of NPs on cellular uptake capacity. Both bared and citrate modified Eu:HAp NPs do not show any significant toxicity in HEK-293 and MDA-MB-231 cell lines. Also, cells treated with citrate modified Eu:HAp NPs exhibits more red-color luminescence in confocal images and enhanced cellular uptake in FACS analysis compared to bared Eu:HAp NPs treatment. Therefore, due to their excellent biocompatibility and cellular uptake, the synthesized NPs are best suited for bioimaging applications. Further, this approach can also be applied for surface modification with various targeting ligands for diverse use.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"80 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098044","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}
Zhiwen Sun, Ji Wang, Qingling Nie, Na Li, Zhihua Liu, Xiao-Juan Yang, Wei Zhao, Biao Wu
The development of energy-efficient sorbents for aqueous CO2 capture remains a significant challenge. This work presents a new design strategy by integrating a tertiary amine (morpholine) with urea motif into a single molecular receptor. This structure enables autonomous, base-free CO2 capture in water, where the urea groups provide complementary hydrogen bonding sites for (bi)carbonate anions, while the morpholine moiety acts as an internal proton acceptor. The resulting receptors demonstrate a rapid uptake of CO2 from a simulated flue gas (10% CO2/N2), achieving a capacity of up to 1.22 mmol/g. Spectroscopic studies (NMR, MS) and structural analysis of a model complex confirm that capture proceeds via hydrogen-bond-stabilized bicarbonate formation. Crucially, the captured CO2 can be completely released under remarkably mild conditions, either by heating ca. 40 °C or by simple N2 purging at ambient temperature. The receptors exhibit excellent recyclability over multiple capture-release cycles without capacity loss. This study highlights the potential of fine-tuning supramolecular interactions-particularly hydrogen bonding combined with a built-in base-to create low-energy, water compatible CO2 capture systems.
{"title":"Bicarbonate anion coordination assisted CO2 capture by using urea-morpholine hybrid receptors in water","authors":"Zhiwen Sun, Ji Wang, Qingling Nie, Na Li, Zhihua Liu, Xiao-Juan Yang, Wei Zhao, Biao Wu","doi":"10.1039/d5dt03056k","DOIUrl":"https://doi.org/10.1039/d5dt03056k","url":null,"abstract":"The development of energy-efficient sorbents for aqueous CO<small><sub>2</sub></small> capture remains a significant challenge. This work presents a new design strategy by integrating a tertiary amine (morpholine) with urea motif into a single molecular receptor. This structure enables autonomous, base-free CO<small><sub>2</sub></small> capture in water, where the urea groups provide complementary hydrogen bonding sites for (bi)carbonate anions, while the morpholine moiety acts as an internal proton acceptor. The resulting receptors demonstrate a rapid uptake of CO<small><sub>2</sub></small> from a simulated flue gas (10% CO<small><sub>2</sub></small>/N<small><sub>2</sub></small>), achieving a capacity of up to 1.22 mmol/g. Spectroscopic studies (NMR, MS) and structural analysis of a model complex confirm that capture proceeds via hydrogen-bond-stabilized bicarbonate formation. Crucially, the captured CO<small><sub>2</sub></small> can be completely released under remarkably mild conditions, either by heating ca. 40 °C or by simple N<small><sub>2</sub></small> purging at ambient temperature. The receptors exhibit excellent recyclability over multiple capture-release cycles without capacity loss. This study highlights the potential of fine-tuning supramolecular interactions-particularly hydrogen bonding combined with a built-in base-to create low-energy, water compatible CO<small><sub>2</sub></small> capture systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101519","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}
Soumi Chakraborty, Erqian Mao, Thomas G. Gray, Thomas S. Teets
To replace precious noble metal-based photosensitizers in applications involving photoinduced charge separation, energy transfer, or photocatalysis, Cu(I) complexes are considered to be cost-effective, earth-abundant, and sustainable alternatives. An emerging and effective design principle in Cu(I) photosensitizers involves heteroleptic structures where the HOMO and LUMO are spatially separated over two different ligands. In the present work, we introduce a complementary class of heteroleptic, three-coordinate copper photosensitizers that pairs variable N^O chelating ligands (8-hydroxyquinoline and 10-hydroxybenzo[h]quinoline) with a bulky 2,6-diisopropylphenyl-substituted N-heterocyclic carbene (NHC). In this design, both frontier orbitals are localized on the same ligand, the N^O chelate, such that structural modulation of the electron-rich N^O-chelates can substantially tune the energy levels of the HOMO and LUMO, thereby controlling the photoluminescence properties. Detailed photophysical and electrochemical experiments as well as DFT calculations suggest charge-transfer transitions with intra-ligand charge transfer (ILCT) character, involving the N^O ligands. This strategy successfully produced long triplet excited-state lifetimes (up to 44 µs) in compounds that are strong photoreductants (E([Cu]+/*[Cu] as negative as −2.0 V vs. the ferrocenium/ferrocene couple). These properties allow these photosensitizers to be used as photocatalysts in various transformations of organic compounds, such as hydrogenation of substituted benzophenones, hydrodehalogenation of aryl/alkyl halides (including challenging C–Cl bond activation) and E/Z isomerization of (E)-stilbene (an example of triplet–triplet energy transfer).
{"title":"Luminescent N-heterocyclic carbene Cu(I) complexes with N^O chelating ligands exhibit microsecond lifetimes and photocatalytic activity","authors":"Soumi Chakraborty, Erqian Mao, Thomas G. Gray, Thomas S. Teets","doi":"10.1039/d5dt02991k","DOIUrl":"https://doi.org/10.1039/d5dt02991k","url":null,"abstract":"To replace precious noble metal-based photosensitizers in applications involving photoinduced charge separation, energy transfer, or photocatalysis, Cu(<small>I</small>) complexes are considered to be cost-effective, earth-abundant, and sustainable alternatives. An emerging and effective design principle in Cu(<small>I</small>) photosensitizers involves heteroleptic structures where the HOMO and LUMO are spatially separated over two different ligands. In the present work, we introduce a complementary class of heteroleptic, three-coordinate copper photosensitizers that pairs variable N^O chelating ligands (8-hydroxyquinoline and 10-hydroxybenzo[h]quinoline) with a bulky 2,6-diisopropylphenyl-substituted N-heterocyclic carbene (NHC). In this design, both frontier orbitals are localized on the same ligand, the N^O chelate, such that structural modulation of the electron-rich N^O-chelates can substantially tune the energy levels of the HOMO and LUMO, thereby controlling the photoluminescence properties. Detailed photophysical and electrochemical experiments as well as DFT calculations suggest charge-transfer transitions with intra-ligand charge transfer (ILCT) character, involving the N^O ligands. This strategy successfully produced long triplet excited-state lifetimes (up to 44 µs) in compounds that are strong photoreductants (<em>E</em>([Cu]<small><sup>+</sup></small>/*[Cu] as negative as −2.0 V <em>vs.</em> the ferrocenium/ferrocene couple). These properties allow these photosensitizers to be used as photocatalysts in various transformations of organic compounds, such as hydrogenation of substituted benzophenones, hydrodehalogenation of aryl/alkyl halides (including challenging C–Cl bond activation) and <em>E</em>/<em>Z</em> isomerization of (<em>E</em>)-stilbene (an example of triplet–triplet energy transfer).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"16 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098039","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}
Nafees Ahmad, Greesh Kumar, Haq Faridi, Ramendra Sundar Dey
The development of cost-effective and multifunctional nanocatalysts is essential to address pressing environmental and energy challenges, particularly organic pollutant removal and sustainable hydrogen production. Herein, we report a ternary nanocomposite comprising polypyrrole (PPy), tungsten trioxide (WO₃), and multiwalled carbon nanotubes (MWCNTs), synthesized and evaluated for dual catalytic applications. The PPy/WO₃/MWCNT composite exhibited remarkable photocatalytic activity toward the degradation of Ponceau BS (PBS) dye under visible light, achieving 98.2% degradation within 40 min following first order kinetics. Adsorption kinetics and isotherm analyses indicated monolayer adsorption behavior with a maximum capacity of 124.6 mg g⁻¹, well described by the Langmuir model (R² = 0.99). The heterojunction between PPy and WO₃ facilitated efficient charge separation, active sites and extended light absorption, while MWCNTs provided conductive pathways and electron reservoirs. Beyond photocatalysis, the composite demonstrated outstanding electrocatalytic activity for overall water splitting in alkaline media, requiring an overpotential of only 146 mV for the hydrogen evolution reaction (HER) and 328 mV for the oxygen evolution reaction (OER) to achieve 10 mA cm⁻². The superior performance is attributed to the synergistic combination of high surface area, enhanced charge transfer kinetics, and multiple redox-active sites. Furthermore, the nanocomposite exhibited excellent long-term stability under both HER and OER conditions, highlighting its promise as a sustainable multifunctional catalyst for environmental remediation and clean energy conversion.
开发具有成本效益和多功能的纳米催化剂对于解决紧迫的环境和能源挑战至关重要，特别是有机污染物去除和可持续制氢。在这里，我们报告了一种三元纳米复合材料，包括聚吡咯（PPy）、三氧化钨（WO₃）和多壁碳纳米管（MWCNTs），合成并评估了双催化应用。PPy/WO₃/MWCNT复合材料在可见光下对Ponceau BS （PBS）染料的降解表现出了显著的光催化活性，在40 min内达到了98.2%的一级降解动力学。吸附动力学和等温线分析表明，它的最大吸附量为124.6 mg g - 1，用Langmuir模型（R²= 0.99）描述得很好。PPy和WO₃之间的异质结促进了有效的电荷分离、活性位点和扩展的光吸收，而MWCNTs提供了导电途径和电子储存器。除了光催化之外，该复合材料在碱性介质中表现出出色的电催化活性，析氢反应（HER）只需要146 mV的过电位，析氧反应（OER）只需要328 mV的过电位就可以达到10 mA cm⁻²。优异的性能归功于高表面积、增强的电荷转移动力学和多个氧化还原活性位点的协同结合。此外，该纳米复合材料在HER和OER条件下均表现出优异的长期稳定性，突显了其作为环境修复和清洁能源转化的可持续多功能催化剂的前景。
{"title":"Synergistic Ternary Polypyrrole/WO₃/MWCNT Nanocomposites for Environmental Remediation and Electrochemical Water Splitting","authors":"Nafees Ahmad, Greesh Kumar, Haq Faridi, Ramendra Sundar Dey","doi":"10.1039/d5dt02347e","DOIUrl":"https://doi.org/10.1039/d5dt02347e","url":null,"abstract":"The development of cost-effective and multifunctional nanocatalysts is essential to address pressing environmental and energy challenges, particularly organic pollutant removal and sustainable hydrogen production. Herein, we report a ternary nanocomposite comprising polypyrrole (PPy), tungsten trioxide (WO₃), and multiwalled carbon nanotubes (MWCNTs), synthesized and evaluated for dual catalytic applications. The PPy/WO₃/MWCNT composite exhibited remarkable photocatalytic activity toward the degradation of Ponceau BS (PBS) dye under visible light, achieving 98.2% degradation within 40 min following first order kinetics. Adsorption kinetics and isotherm analyses indicated monolayer adsorption behavior with a maximum capacity of 124.6 mg g⁻¹, well described by the Langmuir model (R² = 0.99). The heterojunction between PPy and WO₃ facilitated efficient charge separation, active sites and extended light absorption, while MWCNTs provided conductive pathways and electron reservoirs. Beyond photocatalysis, the composite demonstrated outstanding electrocatalytic activity for overall water splitting in alkaline media, requiring an overpotential of only 146 mV for the hydrogen evolution reaction (HER) and 328 mV for the oxygen evolution reaction (OER) to achieve 10 mA cm⁻². The superior performance is attributed to the synergistic combination of high surface area, enhanced charge transfer kinetics, and multiple redox-active sites. Furthermore, the nanocomposite exhibited excellent long-term stability under both HER and OER conditions, highlighting its promise as a sustainable multifunctional catalyst for environmental remediation and clean energy conversion.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"30 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098041","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 new Pd(II) catecholato (Cat) complex bearing 5,5'-divinyl-2,2'-bipyridine as an ancillary ligand (complex 2) was synthesized, and its electrochemical behavior in solutions and electropolymerized films was characterized. A comparison of 2 with an analog containing t Bu groups (complex 1) revealed that the introduced vinyl groups positively shifted the reduction potential of the bipyridine (Bpy) moiety, in line with the lowered lowest unoccupied molecular orbital, thus redshifting the ligand-to-ligand charge transfer (LL'CT) transition absorption from the Cat to Bpy ligands across the Pd(II) center. Complex 2 exhibits a reversible redox wave for the semiquinone (SQ)/Cat couple in DMF/ nBu4NPF6 . On the other hand, the addition of Cl- substantially changed the voltametric properties, indicating disproportionation between the electrogenerated SQ complexes to the regenerated 2 and ligand dissociation products. In contrast to previous reports on the disproportionation of chemically isolated SQ complexes, we found electrochemical features of the repeated anodic oxidation of regenerated 2 followed by disproportionation. The electropolymerized films of 2 on indium tin oxide electrodes exhibited a widely separated pair of anodic and cathodic peaks, similar to those of monomer 2 in solution. The disproportionation of the constituent complexes in the metallopolymers was spectroelectrochemically monitored by the disappearance of the characteristic LL'CT absorption, indicative of ligand dissociation. These findings provide new insights into the fabrication of redox-active metallopolymer films and their applications, which exploit their electrochemical reactivity and bistability in molecular devices.
{"title":"A Pd(II) catecholato complex bearing 5,5'-divinyl-2,2'-bipyridine: synthesis, characterization, and electrochemical disproportionation in solutions and electropolymerized films","authors":"Rizu Tahara, Kohei Matsuura, Keishiro Tahara","doi":"10.1039/d5dt03022f","DOIUrl":"https://doi.org/10.1039/d5dt03022f","url":null,"abstract":"A new Pd(II) catecholato (Cat) complex bearing 5,5'-divinyl-2,2'-bipyridine as an ancillary ligand (complex <strong>2</strong>) was synthesized, and its electrochemical behavior in solutions and electropolymerized films was characterized. A comparison of <strong>2</strong> with an analog containing t Bu groups (complex <strong>1</strong>) revealed that the introduced vinyl groups positively shifted the reduction potential of the bipyridine (Bpy) moiety, in line with the lowered lowest unoccupied molecular orbital, thus redshifting the ligand-to-ligand charge transfer (LL'CT) transition absorption from the Cat to Bpy ligands across the Pd(II) center. Complex 2 exhibits a reversible redox wave for the semiquinone (SQ)/Cat couple in DMF/ <small><sup><em>n</em></sup></small>Bu<small><sub>4</sub></small>NPF<small><sub>6</sub></small> . On the other hand, the addition of Cl<small><sup>-</sup></small> substantially changed the voltametric properties, indicating disproportionation between the electrogenerated SQ complexes to the regenerated <strong>2</strong> and ligand dissociation products. In contrast to previous reports on the disproportionation of chemically isolated SQ complexes, we found electrochemical features of the repeated anodic oxidation of regenerated <strong>2</strong> followed by disproportionation. The electropolymerized films of <strong>2</strong> on indium tin oxide electrodes exhibited a widely separated pair of anodic and cathodic peaks, similar to those of monomer <strong>2</strong> in solution. The disproportionation of the constituent complexes in the metallopolymers was spectroelectrochemically monitored by the disappearance of the characteristic LL'CT absorption, indicative of ligand dissociation. These findings provide new insights into the fabrication of redox-active metallopolymer films and their applications, which exploit their electrochemical reactivity and bistability in molecular devices.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"241 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116148","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 p-toluenethiolate-bridged diplatinum complex bearing ethylene-bridged bis(N-heterocyclic carbene) ligands, all four acetyl-protected glucopyranosyl wingtip substituents adopt the chair conformation, giving rise to an open structure around the Pt2S2 core that allows the complex to react with a Grignard reagent. In contrast, in the corresponding diplatinum complex with o-xylene-bridged bis(N-heterocyclic carbene) ligands, two of the four acetyl-protected glucopyranosyl groups adopt the twist-boat conformation to relieve the steric repulsion among the wingtip N-substituents, resulting in a covered structure around the Pt2S2 core that inhibits reaction with a Grignard reagent.
{"title":"Flexible steric bulk of sugar wingtip substituents on bis(N-heterocyclic carbene) ligands of diplatinum complexes via chair–twist-boat conformational changes","authors":"Shuhei Nomura, Itsuki Kobayashi, Matsumi Doe, Rika Tanaka, Tamaki Nagasawa, Takanori Nishioka","doi":"10.1039/d6dt00111d","DOIUrl":"https://doi.org/10.1039/d6dt00111d","url":null,"abstract":"In the p-toluenethiolate-bridged diplatinum complex bearing ethylene-bridged bis(N-heterocyclic carbene) ligands, all four acetyl-protected glucopyranosyl wingtip substituents adopt the chair conformation, giving rise to an open structure around the Pt<small><sub>2</sub></small>S<small><sub>2</sub></small> core that allows the complex to react with a Grignard reagent. In contrast, in the corresponding diplatinum complex with o-xylene-bridged bis(N-heterocyclic carbene) ligands, two of the four acetyl-protected glucopyranosyl groups adopt the twist-boat conformation to relieve the steric repulsion among the wingtip N-substituents, resulting in a covered structure around the Pt2S2 core that inhibits reaction with a Grignard reagent.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"53 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089595","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}
David Rich, Khusbu Rai, Dinesh Upreti, Jin Hu, Fei Wang, Jian Wang
In this work, we report the synthesis, crystal growth, optical and magnetic properties of two new isotypic bimetallic thiocyanates, MnBi(SCN)5 and CdBi(SCN)5. The crystal structure of MnBi(SCN)5 and CdBi(SCN)5 was determined by single-crystal X-ray diffraction. MnBi(SCN)5 and CdBi(SCN)5 crystallize in the triclinic space group P1 @#x0305; (no.2) with unit cell parameters of a = 8.0498(5) Å, b = 9.2749(5) Å, c = 10.7779(8) Å, α = 72.752(6) °, β = 68.422(6) °, γ = 87.908(5) ° and a = 8.1528(5) Å, b = 9.4008(7) Å, c = 10.9513(8) Å, α = 73.212(6) °, β = 67.963(6) °, γ = 87.879(6) °, respectively. The structure of MnBi(SCN)5 and CdBi(SCN)5 contains a three-dimensional (3D) network consisting of pairs of edge-sharing [TN6] (T = Mn, Cd) linked through the thiocyanate ligand to similar pairs of edge-sharing [BiS6] octahedra. A known related structure to this is that of FeBi(SCN)6, which features a perovskite-like structure consisting of corner-sharing [FeN6] and [BiS6] octahedra. In this work, the magnetic properties of MnBi(SCN)5 and the previously reported FeBi(SCN)6 were investigated, with the former being found to order antiferromagnetically with a Néel temperature around 12K. FeBi(SCN)6 was found to exhibit no magnetic ordering down to 2K, although isothermal magnetization data indicate that it may order ferromagnetically below 2K. Density functional theory (DFT) was also employed to explore the electronic structure of MnBi(SCN)5, which reveals that the Bi-S and Mn-N interactions are crucial for controlling the optical properties of MnBi(SCN)5. MnBi(SCN)5 was predicted to be an indirect semiconductor with a band gap of 2.7 eV, which was reasonably consistent with the UV-Vis spectrum measurement of 2.1 eV.
本文报道了两种新型同型双金属硫氰酸盐MnBi(SCN)5和CdBi(SCN)5的合成、晶体生长、光学和磁性能。采用单晶x射线衍射法测定了MnBi(SCN)5和CdBi(SCN)5的晶体结构。MnBi(SCN)5和CdBi(SCN)5在三斜空间群P1 @#x0305中结晶；(2)与晶胞参数= 8.0498 (5),b = 9.2749 (5) a, c = 10.7779(8),α= 72.752(6)°,β= 68.422(6)°,γ= 87.908(5)°和= 8.1528 (5),b = 9.4008 (7) a, c = 10.9513(8),α= 73.212(6)°,β= 67.963(6)°,分别γ= 87.879(6)°。MnBi(SCN)5和CdBi(SCN)5的结构包含一个三维（3D）网络，由对边共享[TN6] （T = Mn, Cd）通过硫氰酸盐配体连接到相似的对边共享[BiS6]八面体组成。与此相关的已知结构是FeBi(SCN)6，其特征是由共享角的[FeN6]和[BiS6]八面体组成的钙钛矿状结构。在这项工作中，研究了MnBi(SCN)5和先前报道的FeBi(SCN)6的磁性，发现前者在n温度约为12K时具有反铁磁性。FeBi(SCN)6在2K以下没有磁性有序，尽管等温磁化数据表明它在2K以下可能具有铁磁性有序。利用密度泛函理论（DFT）研究了MnBi(SCN)5的电子结构，揭示了Bi-S和Mn-N相互作用对MnBi(SCN)5光学性质的控制至关重要。预测MnBi(SCN)5为间接半导体，带隙为2.7 eV，与2.1 eV的紫外可见光谱测量值基本一致。
{"title":"Synthesis, Crystal Growth, Optical and Magnetic Properties of Three Bimetallic Thiocyanates TBi(SCN)5(T=Mn, Cd) and FeBi(SCN)6","authors":"David Rich, Khusbu Rai, Dinesh Upreti, Jin Hu, Fei Wang, Jian Wang","doi":"10.1039/d5dt02869h","DOIUrl":"https://doi.org/10.1039/d5dt02869h","url":null,"abstract":"In this work, we report the synthesis, crystal growth, optical and magnetic properties of two new isotypic bimetallic thiocyanates, MnBi(SCN)<small><sub>5</sub></small><small><sub></sub></small> and CdBi(SCN)<small><sub>5</sub></small>. The crystal structure of MnBi(SCN)<small><sub>5</sub></small> and CdBi(SCN)<small><sub>5</sub></small> was determined by single-crystal X-ray diffraction. MnBi(SCN)<small><sub>5</sub></small> and CdBi(SCN)<small><sub>5</sub></small> crystallize in the triclinic space group P1 @#x0305; (no.2) with unit cell parameters of a = 8.0498(5) Å, b = 9.2749(5) Å, c = 10.7779(8) Å, α = 72.752(6) °, β = 68.422(6) °, γ = 87.908(5) ° and a = 8.1528(5) Å, b = 9.4008(7) Å, c = 10.9513(8) Å, α = 73.212(6) °, β = 67.963(6) °, γ = 87.879(6) °, respectively. The structure of MnBi(SCN)<small><sub>5</sub></small> and CdBi(SCN)<small><sub>5</sub></small> contains a three-dimensional (3D) network consisting of pairs of edge-sharing [TN<small><sub>6</sub></small>] (T = Mn, Cd) linked through the thiocyanate ligand to similar pairs of edge-sharing [BiS<small><sub>6</sub></small>] octahedra. A known related structure to this is that of FeBi(SCN)<small><sub>6</sub></small>, which features a perovskite-like structure consisting of corner-sharing [FeN<small><sub>6</sub></small>] and [BiS<small><sub>6</sub></small>] octahedra. In this work, the magnetic properties of MnBi(SCN)<small><sub>5</sub></small> and the previously reported FeBi(SCN)<small><sub>6</sub></small> were investigated, with the former being found to order antiferromagnetically with a Néel temperature around 12K. FeBi(SCN)<small><sub>6</sub></small> was found to exhibit no magnetic ordering down to 2K, although isothermal magnetization data indicate that it may order ferromagnetically below 2K. Density functional theory (DFT) was also employed to explore the electronic structure of MnBi(SCN)<small><sub>5</sub></small>, which reveals that the Bi-S and Mn-N interactions are crucial for controlling the optical properties of MnBi(SCN)<small><sub>5</sub></small>. MnBi(SCN)<small><sub>5</sub></small> was predicted to be an indirect semiconductor with a band gap of 2.7 eV, which was reasonably consistent with the UV-Vis spectrum measurement of 2.1 eV.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089633","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}
Larissa Chimilouski, Sheetal Ranaut, William Henrique Slominski, Patrícia Salvador Tessaro, Gilson de Freitas Silva, Edmar Martendal, Claudio Verani, Shivnath Mazumder, Fernando R Xavier
The oxidation of p-substituted benzyl alcohols by metallated tetraphenylporphyrin catalysts [MnIII(TPP)Cl] (1) and [FeIII(TPP)Cl] (2) in presence of the oxidizing agent (diacetoxyiodo)benzene (DAIB) was evaluated by means of an integrated approach considering the experimental results under the light of a three-level full factorial design (FFD) and density functional theory (DFT) analysis. Aiming to promote and maximize the formation of benzaldehyde and benzoic acid, the use of multivariate analysis allows us to study the interactivity and interplay between critical variables such as catalyst load (mol%) and time (minutes). On the one hand, benzaldehyde formation was optimized when 4.0 mol% of 1 catalyzed the reaction for 90 minutes or when 2.8 mol% of 2 catalyzed the reaction for 100 minutes. On the other hand, benzoic acid formation was favored when 5.0 mol% of 1 was used over 90 minutes or 4.8 mol% of 2 over 60 minutes. Several control tests were performed to verify the catalytic nature of the metalloporphyrins, including the use of butylated hydroxytoluene to confirm the presence of radical species involved in the catalytic process. The possible mechanisms, as well as the electronic structures of the main reaction intermediates were assessed by means of DFT calculations and benchmarked against the experimental data and available literature. Catalysts 1 and 2 display subtle but distinct mechanistic pathways that explain the observed differences in chemical reactivity. Additionally, different linear free energy relationships associated with distinct spin densities of transition states were observed during the determinant step when p-substituted R-benzyl alcohol substrates containing R = OMe, H, Cl, NO2 were considered.
{"title":"A comprehensive experimental, multivariate statistical, and DFT computational analysis of the catalytic oxidation of benzyl alcohols mediated by Mn(III) and Fe(III) metalloporphyrins","authors":"Larissa Chimilouski, Sheetal Ranaut, William Henrique Slominski, Patrícia Salvador Tessaro, Gilson de Freitas Silva, Edmar Martendal, Claudio Verani, Shivnath Mazumder, Fernando R Xavier","doi":"10.1039/d5dt02798e","DOIUrl":"https://doi.org/10.1039/d5dt02798e","url":null,"abstract":"The oxidation of p-substituted benzyl alcohols by metallated tetraphenylporphyrin catalysts [MnIII(TPP)Cl] (1) and [FeIII(TPP)Cl] (2) in presence of the oxidizing agent (diacetoxyiodo)benzene (DAIB) was evaluated by means of an integrated approach considering the experimental results under the light of a three-level full factorial design (FFD) and density functional theory (DFT) analysis. Aiming to promote and maximize the formation of benzaldehyde and benzoic acid, the use of multivariate analysis allows us to study the interactivity and interplay between critical variables such as catalyst load (mol%) and time (minutes). On the one hand, benzaldehyde formation was optimized when 4.0 mol% of 1 catalyzed the reaction for 90 minutes or when 2.8 mol% of 2 catalyzed the reaction for 100 minutes. On the other hand, benzoic acid formation was favored when 5.0 mol% of 1 was used over 90 minutes or 4.8 mol% of 2 over 60 minutes. Several control tests were performed to verify the catalytic nature of the metalloporphyrins, including the use of butylated hydroxytoluene to confirm the presence of radical species involved in the catalytic process. The possible mechanisms, as well as the electronic structures of the main reaction intermediates were assessed by means of DFT calculations and benchmarked against the experimental data and available literature. Catalysts 1 and 2 display subtle but distinct mechanistic pathways that explain the observed differences in chemical reactivity. Additionally, different linear free energy relationships associated with distinct spin densities of transition states were observed during the determinant step when p-substituted R-benzyl alcohol substrates containing R = OMe, H, Cl, NO2 were considered.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"42 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095761","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 catalytic performance of single-atom Pt1/Co3O4 catalysts in the selective hydrogenation of cinnamaldehyde (CAL) is systematically investigated with a focus on crystal facet effects. Three distinct Co3O4 morphologies—cubic (Co3O4-c), truncated octahedral (Co3O4-t), and octahedral (Co3O4-o)—are synthesized to expose different facets. Among them, Pt1/Co3O4-c exhibits superior selectivity (78.1% towards cinnamyl alcohol) and conversion (97.8%) under mild conditions. Structural characterizations combined with density functional theory (DFT) calculations reveal that the exposed (100) facets in Co3O4-c promote stronger electron transfer to Pt single atoms, enhancing the preferential hydrogenation of the C=O bond over the C=C bond. These findings provide valuable insights into facet-dependent electronic modulation in single-atom catalysis, facilitating the rational design of efficient catalysts for selective hydrogenation.
{"title":"Crystal Facet Engineering of Pt1/Co3O4 Single-Atom Catalysts for Highly Selective Hydrogenation of Cinnamaldehyde","authors":"Liyun Huang, Zheng Zhang, Qingdi Sun, Huanshi Lan, Xiaohui He, Liangbin Wang","doi":"10.1039/d5dt02227d","DOIUrl":"https://doi.org/10.1039/d5dt02227d","url":null,"abstract":"The catalytic performance of single-atom Pt1/Co3O4 catalysts in the selective hydrogenation of cinnamaldehyde (CAL) is systematically investigated with a focus on crystal facet effects. Three distinct Co3O4 morphologies—cubic (Co3O4-c), truncated octahedral (Co3O4-t), and octahedral (Co3O4-o)—are synthesized to expose different facets. Among them, Pt1/Co3O4-c exhibits superior selectivity (78.1% towards cinnamyl alcohol) and conversion (97.8%) under mild conditions. Structural characterizations combined with density functional theory (DFT) calculations reveal that the exposed (100) facets in Co3O4-c promote stronger electron transfer to Pt single atoms, enhancing the preferential hydrogenation of the C=O bond over the C=C bond. These findings provide valuable insights into facet-dependent electronic modulation in single-atom catalysis, facilitating the rational design of efficient catalysts for selective hydrogenation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070568","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 impact of subtle modification of the environment on magnetic properties, by exchanging only solvent molecules, was investigated using a novel series of cobalt(II) compounds as a case study. Three new cobalt(II) complexes with phenanthroline ligand (phen) and chloranilic acid (CA) [Co(CA)(phen)2] (1) were synthesized:1·MeOH, 1·EtOH, and 1·EtGly. A single-crystal and powder X-ray diffraction revealed that all structures are isostructural mononuclear complexes with a distorted octahedral cobalt environment. X-band ESR spectroscopy provided an effective spin of 1/2 with anisotropic ge f f -values for cobalt ions at low temperatures. ESR linewidth analysis, supported by DFT calculations, revealed negligible intermolecular interactions. Static magnetic properties were studied using the temperature- and field-dependence of magnetization. Comprehensive magnetic modeling of the experimental data, provides deeper insight into the subtle influence of different crystal packing arising from solvent exchange on the magnetic properties of the complexes. Additionally, AC magnetic susceptibility studies at low temperatures revealed field-induced slow magnetization relaxation in these cobalt(II) compounds.
{"title":"Magneto-structural correlations in cobalt(II)-phenanthroline compounds with chloranilic acid","authors":"Filip Torić, Lidija Androš Dubraja, Mirta Herak, Nikolina Novosel, Irina Petreska, Kresimir Molcanov, Dijana Žilić","doi":"10.1039/d5dt02533h","DOIUrl":"https://doi.org/10.1039/d5dt02533h","url":null,"abstract":"The impact of subtle modification of the environment on magnetic properties, by exchanging only solvent molecules, was investigated using a novel series of cobalt(II) compounds as a case study. Three new cobalt(II) complexes with phenanthroline ligand (phen) and chloranilic acid (CA) [Co(CA)(phen)<small><sub>2</sub></small>] (<strong>1</strong>) were synthesized:<strong>1</strong>·MeOH, <strong>1</strong>·EtOH, and <strong>1</strong>·EtGly. A single-crystal and powder X-ray diffraction revealed that all structures are isostructural mononuclear complexes with a distorted octahedral cobalt environment. X-band ESR spectroscopy provided an effective spin of 1/2 with anisotropic <em>g</em><small><sub>e f f </sub></small>-values for cobalt ions at low temperatures. ESR linewidth analysis, supported by DFT calculations, revealed negligible intermolecular interactions. Static magnetic properties were studied using the temperature- and field-dependence of magnetization. Comprehensive magnetic modeling of the experimental data, provides deeper insight into the subtle influence of different crystal packing arising from solvent exchange on the magnetic properties of the complexes. Additionally, AC magnetic susceptibility studies at low temperatures revealed field-induced slow magnetization relaxation in these cobalt(II) compounds.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"272 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070567","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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