Development of metallic conduction and molecular insertion in one-dimensional metal complexes

一维金属配合物中金属传导和分子插入的发展

• 批准号: 18J13022
• 负责人: Mian Mohammad Rasel
• 金额: $ 0.96万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2018
• 资助国家: 日本
• 起止时间: 2018-04-25 至 2020-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-18J13022/
• 关键词: crystalligraphy; synthesis; coordination polymer; chain complex; metal-organic-framework; conductivity; catalysis; gas uptake; One-dimension sysmetm; Pd chain; Pt chain; halogen-bridged; infinite structure; optical gap; Raman spectrocopy

Recently, organic-inorganic hybrids materials have been researchers’ interest due to their tunable structure and switching physical properties. Solid-state hybrid materials are very promising in the field for fundamental and applied sciences.I prepared halogen-bridged 1D Pd/Pt chain complexes (MX-chain) as multifunctional materials. Pd and Pt-based MX-chain complexes usually show M(II)/M(IV) mixed-valance (MV) state due to the small on-site coulomb repulsion. I developed new method for realize uncommon Pd(III) AV state, [Pd(dabdOH)2Br]Br2 (dabdOH =(2S,3S)-2,3-diaminobutane-1,4-diol), so-called "multiple-hydogen-bond” approach (J. Am. Chem. Soc. 2017, 39, 6562). Electronic state Pt ions are in MV state using same strategy. However, this method is very promising for shortening metal-metal distance, resulting good conducting materials (Inorg. Chem, 2019, 58, 114). Moreover, this method is also applicable for large size counters anion. Pd(III) ions was isolated with sulfate ions via this method (CryEngComm, 2020, Submitted).Currently, I extended my work into two or three-dimensional (2D or 3D) hybrid materials (MOFs). I was able to growth and control copper nano particle (CuNPs) size into MOFs. For example, NU-901 and NU-907, with distinct pore diameters that serve as templates for the controlled growth of CuNPs of different sizes (~1.5 nm and ~0.9 nm, respectively). These MOF-supported CuNPs were shown to be competent catalysts for selective acetylene semihydrogenation with a TOF of 13.5 and 7.7 h-1, respectively (Chem. Mat. 2020, 10.1021/acs.chemmater.0c00059).

近年来，有机-无机杂化材料由于其结构可调、物理性能可调等特点，引起了人们的广泛关注。固态杂化材料在基础科学和应用科学领域都有着广阔的应用前景，本文制备了卤素桥联的一维Pd/Pt链状配合物（MX-链）。Pd和Pt基MX链配合物由于在位库仑排斥小，通常表现为M（II）/M（IV）混合价态。我发展了一种实现Pd（III）AV态的新方法，[Pd（dabdOH）2Br] Br 2（dabdOH =（2S，3S）-2，3-diaminodutane-1，4-diol），即所谓的“多氢键”方法（J. Am. 2017，39，6562）。电子态Pt离子使用相同的策略处于MV态。然而，这种方法非常有希望缩短金属-金属距离，从而产生良好的导电材料（Inorg. Chem，2019，58，114）。该方法也适用于大型阴离子计数器。通过这种方法将Pd（III）离子与硫酸根离子分离（CryEngComm，2020，Submitted）。目前，我将我的工作扩展到二维或三维（2D或3D）杂化材料（MOFs）。我能够生长和控制铜纳米颗粒（CuNPs）的大小到MOF中。例如，NU-901和NU-907具有不同的孔径，可作为不同尺寸（分别为~1.5 nm和~0.9 nm）的CuNP受控生长的模板。这些MOF负载的CuNP显示为分别具有13.5和7.7h-1的TOF的选择性乙炔半氢化的胜任催化剂（Chem.Mat.Chem.Sci. 0c00059）。

项目成果

Multiple-Hydrogen-Bond Approach to Control the Oxidation State of Pd in MX Complexes

控制 MX 配合物中 Pd 氧化态的多重氢键方法

• 发表时间: 2018
• 作者: Mohammad Rasel Mian;Masahiro Yamashita
• 通讯作者: Masahiro Yamashita

Precise Control of Cu Nanoparticle Size and Catalytic Activity through Pore Templating in Zr Metal-Organic Frameworks

• DOI: 10.1021/acs.chemmater.0c00059
• 发表时间: 2020-04-14
• 期刊: CHEMISTRY OF MATERIALS
• 影响因子: 8.6
• 作者: Mian, Mohammad Rasel;Redfern, Louis R.;Farha, Omar K.
• 通讯作者: Farha, Omar K.

MX-type single chain complexes with an aromatic in-plane ligand: incorporation of aromatic interactions for stabilizing the chain structure

具有芳香族面内配体的 MX 型单链配合物：引入芳香族相互作用以稳定链结构

• DOI: 10.1039/c9dt00784a
• 发表时间: 2019
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Afrin Unjila;Iguchi Hiroaki;Mian Mohammad Rasel;Takaishi Shinya;Yamakawa Hiromichi;Terashige Tsubasa;Miyamoto Tatsuya;Okamoto Hiroshi;Yamashita Masahiro
• 通讯作者: Yamashita Masahiro

Tuning the Redox Activity of Metal-Organic Frameworks for Enhanced, Selective O2 Binding: Design Rules and Ambient Temperature O2 Chemisorption in a Cobalt-Triazolate Framework

• DOI: 10.1021/jacs.9b12401
• 发表时间: 2020-03-04
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Rosen, Andrew S.;Mian, M. Rasel;Snurr, Randall Q.
• 通讯作者: Snurr, Randall Q.

Observation of charge bistability in quasi-one-dimensional halogen-bridged palladium complexes by X-ray absorption spectroscopy

X射线吸收光谱观察准一维卤桥钯配合物的电荷双稳定性

• DOI: 10.1039/c9dt01684h
• 发表时间: 2019
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Takefumi Yoshida;Shinya Takaishi;Shohei Kumagai;Hiroaki Iguchi;Mohammad Rasel Mian;Masahiro Yamashita
• 通讯作者: Masahiro Yamashita