Balendra, Rahul Kalita, Mahboob Ali, Sanyukta, Sevi Murugavel and Kuntal Manna
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Mn-CP1 exhibited a high dielectric constant at room temperature (<em>κ</em> ≈ 12.2 at 1 kHz), attributed to the combined effects of its polar metal-carboxylate framework and the orientational polarization of coordinated and lattice DMF molecules. Upon thermal desolvation of Mn-CP1, the dielectric constant sharply decreases to <em>κ</em> ≈ 4.4, demonstrating polar solvent-responsive dielectric tunability. Impedance spectroscopy (<em>Z</em>′ and <em>Z</em>′′) further confirmed that observed changes in dielectric properties arise from intrinsic bulk properties and framework host interactions. In addition to dielectric behaviour, Mn-CP1 also displayed excellent catalytic performance for the selective oxidation of methylarenes to arylaldehydes under mild conditions, achieving 83% conversion and 88% selectivity for toluene using H<small><sub>2</sub></small>O<small><sub>2</sub></small> as a green oxidant. These results highlight Mn-CP1 as a multifunctional material that combines solvent-tunable dielectric behavior with catalytic efficiency, offering strong potential for applications in electronic devices and sustainable catalysis.</p>","PeriodicalId":84,"journal":{"name":"Journal of Materials Chemistry C","volume":" 41","pages":" 21122-21131"},"PeriodicalIF":5.1000,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A multifunctional manganese coordination polymer with polar solvent-responsive tunable dielectric properties and selective catalysis\",\"authors\":\"Balendra, Rahul Kalita, Mahboob Ali, Sanyukta, Sevi Murugavel and Kuntal Manna\",\"doi\":\"10.1039/D5TC02227D\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A dielectric-tunable coordination polymer, [Mn<small><sub>2</sub></small>(SBA)<small><sub>2</sub></small>(Phen)(DMF)]·2DMF (Mn-CP1), has been synthesized <em>via</em> solvothermal method using manganese salt, 4,4′-sulfonyldibenzoic acid (H<small><sub>2</sub></small>SBA), 1,10-phenanthroline (Phen), and DMF–MeOH solvent system. Single-crystal X-ray diffraction of Mn-CP1 revealed a well-defined 2D square-channel framework constructed from rare tetranuclear {Mn<small><sub>4</sub></small>N<small><sub>4</sub></small>O<small><sub>18</sub></small>} secondary building units within the triclinic <em>P</em><img> space group. Mn-CP1 exhibited a high dielectric constant at room temperature (<em>κ</em> ≈ 12.2 at 1 kHz), attributed to the combined effects of its polar metal-carboxylate framework and the orientational polarization of coordinated and lattice DMF molecules. Upon thermal desolvation of Mn-CP1, the dielectric constant sharply decreases to <em>κ</em> ≈ 4.4, demonstrating polar solvent-responsive dielectric tunability. Impedance spectroscopy (<em>Z</em>′ and <em>Z</em>′′) further confirmed that observed changes in dielectric properties arise from intrinsic bulk properties and framework host interactions. 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引用次数: 0
摘要
以锰盐、4,4′-磺基二苯甲酸(H2SBA)、1,10-菲罗啉(Phen)和DMF - meoh为溶剂体系,采用溶剂热法合成了一种介电可调配位聚合物[Mn2(SBA)2(Phen)(DMF)]·2DMF (Mn-CP1)。Mn-CP1的单晶x射线衍射显示,在三斜位P空间群中,由稀有的四核{Mn4N4O18}二级结构单元构建了一个明确的二维方形通道框架。Mn-CP1在室温下具有较高的介电常数(κ≈12.2 at 1 kHz),这是由于其极性金属-羧酸盐框架以及配位和点阵DMF分子的取向极化的共同作用。Mn-CP1热脱溶后,介电常数急剧下降至κ≈4.4,表现出极性溶剂响应介电可调性。阻抗谱(Z '和Z ")进一步证实了所观察到的介电性质的变化是由固有体性质和框架宿主相互作用引起的。除了介电性能外,Mn-CP1在温和条件下对甲基芳烃选择性氧化为芳醛也表现出优异的催化性能,在H2O2作为绿色氧化剂的情况下,对甲苯的转化率达到83%,选择性达到88%。这些结果突出了Mn-CP1作为一种结合了溶剂可调介电行为和催化效率的多功能材料,在电子器件和可持续催化方面具有强大的应用潜力。
A multifunctional manganese coordination polymer with polar solvent-responsive tunable dielectric properties and selective catalysis
A dielectric-tunable coordination polymer, [Mn2(SBA)2(Phen)(DMF)]·2DMF (Mn-CP1), has been synthesized via solvothermal method using manganese salt, 4,4′-sulfonyldibenzoic acid (H2SBA), 1,10-phenanthroline (Phen), and DMF–MeOH solvent system. Single-crystal X-ray diffraction of Mn-CP1 revealed a well-defined 2D square-channel framework constructed from rare tetranuclear {Mn4N4O18} secondary building units within the triclinic P space group. Mn-CP1 exhibited a high dielectric constant at room temperature (κ ≈ 12.2 at 1 kHz), attributed to the combined effects of its polar metal-carboxylate framework and the orientational polarization of coordinated and lattice DMF molecules. Upon thermal desolvation of Mn-CP1, the dielectric constant sharply decreases to κ ≈ 4.4, demonstrating polar solvent-responsive dielectric tunability. Impedance spectroscopy (Z′ and Z′′) further confirmed that observed changes in dielectric properties arise from intrinsic bulk properties and framework host interactions. In addition to dielectric behaviour, Mn-CP1 also displayed excellent catalytic performance for the selective oxidation of methylarenes to arylaldehydes under mild conditions, achieving 83% conversion and 88% selectivity for toluene using H2O2 as a green oxidant. These results highlight Mn-CP1 as a multifunctional material that combines solvent-tunable dielectric behavior with catalytic efficiency, offering strong potential for applications in electronic devices and sustainable catalysis.
期刊介绍:
The Journal of Materials Chemistry is divided into three distinct sections, A, B, and C, each catering to specific applications of the materials under study:
Journal of Materials Chemistry A focuses primarily on materials intended for applications in energy and sustainability.
Journal of Materials Chemistry B specializes in materials designed for applications in biology and medicine.
Journal of Materials Chemistry C is dedicated to materials suitable for applications in optical, magnetic, and electronic devices.
Example topic areas within the scope of Journal of Materials Chemistry C are listed below. This list is neither exhaustive nor exclusive.
Bioelectronics
Conductors
Detectors
Dielectrics
Displays
Ferroelectrics
Lasers
LEDs
Lighting
Liquid crystals
Memory
Metamaterials
Multiferroics
Photonics
Photovoltaics
Semiconductors
Sensors
Single molecule conductors
Spintronics
Superconductors
Thermoelectrics
Topological insulators
Transistors