Layered Simple Hydroxides Functionalized by Fluorene-Phosphonic Acids: Synthesis, Interface Theoretical Insights, and Magnetoelectric Effect

Evrard Quentin; Chaker Ziyad; Roger Melissa; Sevrain Charlotte M.; Delahaye Emilie; Gallart Mathieu; Gilliot Pierre; Leuvrey Cedric; Rueff Jean-Michel; Rabu Pierre; Massobrio Carlo; Boero Mauro; Pautrat Alain; Jaffres Paul-Alain; Ori Guido; Rogez Guillaume

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Layered Simple Hydroxides Functionalized by Fluorene-Phosphonic Acids: Synthesis, Interface Theoretical Insights, and Magnetoelectric Effect

机译：氟膦酸官能化的层状简单氢氧化物：合成，界面理论的见解和磁电效应

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Copper-and cobalt-based layered simple hydroxides (LSH) are successfully functionalized by a series of fluorene mono- and diphosphonic acids, using anionic exchange reactions and a preintercalation strategy. The lateral functionalization of the fluorene moieties has only little impact on the overall structure of the obtained layered hybrid materials but it influences the organization of the molecules within the interlamellar spacing. For bulky fluorene (9,9-dioctyl derivative), luminescence is preserved when inserted into copper and cobalt hydroxydes, whereas it is completely quenched for the other fluorenes. Detailed characterization of the internal structure and chemical bonding properties for copper-and cobalt-based hybrids is performed via ancillary experimental techniques. For the copper-based LSH class, for which more elusive findings are found, first-principles molecular dynamics simulations unravel the fundamental stabilizing role of the H-bonding network promoted within the local environments of the fluorene mono-and diphosphonic acids. The cobalt series of compounds constitute a new class of hybrid magnets, with ordering temperatures ranging from 11.8 to 17.8 K and show a clear magnetoelectric effect. This effect appears above a threshold magnetic field, which is null below the magnetic ordering temperature, and it persists in the paramagnetic regime till about 110 K.

机译：铜和钴基层状简单氢氧化物（LSH）已通过一系列芴单膦酸和二膦酸使用阴离子交换反应和预嵌入策略成功官能化。芴部分的侧向官能化对所获得的层状杂化材料的整体结构影响很小，但是它影响了层间间距内分子的组织。对于大芴（9,9-二辛基衍生物），当插入铜和钴的羟基化物中时，发光得以保留，而对于其他芴则完全被淬灭。铜和钴基杂化物的内部结构和化学键合特性的详细表征是通过辅助实验技术进行的。对于发现较难发现的铜基LSH类，第一性原理分子动力学模拟揭示了在芴单和二膦酸的局部环境中促进的H键网络的基本稳定作用。钴系列化合物构成一类新的混合磁体，其订购温度范围为11.8至17.8 K，并显示出清晰的磁电效应。该效应出现在阈值磁场之上，该阈值磁场在磁有序温度以下为零，并且在顺磁状态下一直持续到大约110K。

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来源
《Advanced Functional Materials》 |2017年第41期|1703576.1-1703576.13|共13页
作者
Evrard Quentin; Chaker Ziyad; Roger Melissa; Sevrain Charlotte M.; Delahaye Emilie; Gallart Mathieu; Gilliot Pierre; Leuvrey Cedric; Rueff Jean-Michel; Rabu Pierre; Massobrio Carlo; Boero Mauro; Pautrat Alain; Jaffres Paul-Alain; Ori Guido; Rogez Guillaume;
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作者单位

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

Univ Brest, IBSAM, CNRS UMR 6521, CEMCA, 6 Ave Victor Le Gorgeu, F-29238 Brest, France;

Univ Brest, IBSAM, CNRS UMR 6521, CEMCA, 6 Ave Victor Le Gorgeu, F-29238 Brest, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

CNRS, ENSICAEN, CRISMAT, UMR 6508, 6 Bd Marechal Juin, F-14050 Caen, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

CNRS, ENSICAEN, CRISMAT, UMR 6508, 6 Bd Marechal Juin, F-14050 Caen, France;

Univ Brest, IBSAM, CNRS UMR 6521, CEMCA, 6 Ave Victor Le Gorgeu, F-29238 Brest, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, F-67034 Strasbourg 2, France;

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正文语种 eng
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关键词
first-principles molecular dynamics; fluorene phosphonic acids; layered simple hydroxides; magnetoelectric effects;

机译：第一性原理分子动力学;芴膦酸;层状简单氢氧化物;磁电效应;

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机译：基于层状简单氢氧化物主体和离子液体客体的功能性杂化材料的插层合成-通往没有硅胶基质的多功能离子凝胶的途径？
2. Rational synthesis of chiral layered magnets by functionalization of metal simple hydroxides with chiral and non-chiral Ni(II) Schiff base complexes [J] . Delahaye E., Eyele-Mezui S., Diop M., Dalton transactions: An international journal of inorganic chemistry . 2010,第44期

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3. One-pot Synthesis of Furfural from Xylose using Al2O3-Ni-Al Layered Double Hydroxide Acid-Base Bi-functional Catalyst and Sulfonated Resin [J] . Shirotori Mahiro, Nishimura Shun, Ebitani Kohki Chemistry Letters . 2016,第2期

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4. Synthesis of Carboxylic Acids Intercalated Mg-Al Layered Double Hydroxides by a Modified Reconstruction Method [C] . Weidong Yang, Sheng Li, Dong Yang Wu, International Symposium on Advanced Synthesis and Processing Technology for Materials . 2009

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5. Adsorption of simple aromatic organic acids/anions at the alumina/water interface: Influence of functionality and background electrolytes. [D] . Borah, Jayanta Madhab. 2010

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6. Insights into the Synthesis of Layered Double Hydroxide (LDH) Nanoparticles: Part 1. Optimization and Controlled Synthesis of Chloride-Intercalated LDH [O] . Xiaodi Sun, Erica Neuperger, Sandwip K. Dey -1

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Layered Simple Hydroxides Functionalized by Fluorene-Phosphonic Acids: Synthesis, Interface Theoretical Insights, and Magnetoelectric Effect

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