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).

最近，有机-无机杂化材料因其可调节的结构和可切换的物理性能而引起了研究人员的兴趣。固态杂化材料在基础科学和应用科学领域非常有前景。我制备了卤桥一维Pd/Pt链配合物（MX链）作为多功能材料。由于较小的现场库仑斥力，Pd 和 Pt 基 MX 链配合物通常呈现 M(II)/M(IV) 混合价态 (MV)。我开发了实现罕见的 Pd(III) AV 态的新方法，[Pd(dabdOH)2Br]Br2 (dabdOH =(2S,3S)-2,3-diaminobutane-1,4-diol)，即所谓的“多重氢键”方法 (J. Am. Chem. Soc. 2017, 39, 6562)。使用相同的策略，电子态 Pt 离子处于 MV 态。然而，这种方法对于缩短金属-金属距离，产生良好的导电材料非常有前景(Inorg. Chem, 2019, 58, 114)。此外，该方法也适用于大尺寸反阴离子。通过这种方法，Pd(III) 离子与硫酸根离子分离（CryEngComm，2020，已提交）。目前，我将工作扩展到二维或三维（2D 或 3D）杂化材料（MOF）。我能够在 MOF 中生长并控制铜纳米颗粒 (CuNP) 的尺寸。例如，NU-901 和 NU-907 具有不同的孔径，可用作不同尺寸（分别为~1.5 nm 和~0.9 nm）CuNP 的受控生长的模板。这些 MOF 负载的 CuNP 被证明是选择性乙炔半氢化的有效催化剂，TOF 分别为 13.5 和 7.7 h-1 (Chem. Mat. 2020, 10.1021/acs.chemmater.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