Science of Nano-Wire Metal Complexes with Strong Electron-Correlation

强电子关联纳米线金属配合物科学

• 批准号: 15GS0216
• 负责人: YAMASHITA Masahiro
• 金额: $ 253.84万
• 依托单位: Tohoku University (2004-2007)Tokyo Metropolitan University (2003)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Creative Scientific Research
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15GS0216/
• 关键词: Third-Order Optical Nonlinearity; Strong Electron Correlation; Electron-Phonon Interaction; Peierls Transition; Nano-Wire; Mott-Insulator; Fastener Effect; Ultra-Fast Optical Communication; 電荷密度波状態; モット絶縁体状態; 相転移; 光誘起相転移; 化学的圧力; ナノワイヤー金属錯体

Quasi-one-dimensional halogen-bridged Pd compounds take a Pd(II)-Pd(IV) mixed-valence state or charge-density-wave state or Peierls Insulator due to the electron-phonon interaction. In order to realize a Pd(III) Mott-Insulator we used the sulphonic acid counter anions with long alkyl chains. In the raw of the five alkyl chain, the Pd compound shows the phase transition from the Pd(II)-Pd(IV) Peierls Insulator into the Pd(III) Mott-Insulator about 200K with hysteresis, which is the inverse Peierls transition. This phenomena were evidenced by ESR, X-ray single-crystal analyses, single-crystal reflection spectra, electrical conductivities, etc. In the case of the ten and twelve alkyl chains, the Pd(III) Mott-insulators are the ground state even in mom temperature, which is the first example. These interesting phenomena are well explained by the fastener effect or chemical pressure of the long alkyl chains. In the Pd(III) Mott-Insulator at 15 K the photo-irradiation with the energy of the charge transfer band (0.5eV) produced the Pd(II)-Pd(IV) Peierls Insulator state, while the photo-irradiation with L5 eV produced the metallic state. Such photo-induced phase transitions occurred in femto-seconds, which are available for the ultra-fast optical communication.

由于电子-声子相互作用，准一维卤素桥联Pd化合物呈现Pd（II）-Pd（IV）混合价态或电荷密度波态或Peierls绝缘体。为了实现Pd（III）莫特绝缘体，我们使用具有长烷基链的磺酸抗衡阴离子。在五烷基链的起始温度下，Pd化合物在200 K左右发生了从Pd（II）-Pd（IV）Peierls绝缘体到Pd（III）Mott绝缘体的相变，该相变具有滞后现象，即逆Peierls相变。ESR、X-射线单晶分析、单晶反射谱、电导率等都证明了这一现象。在10和12个烷基链的情况下，Pd（III）Mott绝缘体即使在室温下也是基态，这是第一个例子。这些有趣的现象很好地解释了紧固件效应或长烷基链的化学压力。在Pd（III）Mott-Insulator体系中，在15 K下，用电荷转移带能量（0.5eV）的光辐照产生Pd（II）-Pd（IV）Peierls绝缘体态，而用L5 eV的光辐照产生金属态。这种光致相变发生在飞秒量级，可用于超快光通信。

项目成果

Single-Chain Magnet(Net_4)[Mn_2(5-MeOsalen)_2Fe(CN)_6] Made of Mn^<III>-Fe^<II>-Mn^<III> Trinuclear Single-Molecule Magnet with an ST=9/2 Spin Ground State

单链磁体(Net_4)[Mn_2(5-MeOsalen)_2Fe(CN)_6] Mn^<III>-Fe^<II>-Mn^<III>三核单分子磁体，ST=9/

• 发表时间: 2005
• 期刊: J.Am.Chem.Soc. 127
• 作者: T. Matsumoto;T. Taguchi;K. Mima;R. Kajitani,;M.Ferbinteanu et al.
• 通讯作者: M.Ferbinteanu et al.

[Mn_2^<III>(5-Rsaltmen)_2Ni^<II>(pao)_2L]^<2+> : An S_T=3 Building Block for a Single-Chain Magnet That Behaves as a Single-Molecule Magnet

[Mn_2^<III>(5-Rsaltmen)_2Ni^<II>(pao)_2L]^<2>：用于单链磁体的 S_T=3 构建块，其行为类似于单分子磁体

• 发表时间: 2005
• 期刊: Chem.Eur.J. 11
• 作者: H. Sakagami;T. Johzaki;H. Nagatomo;K. Mima;H.Miyasaka et al.
• 通讯作者: H.Miyasaka et al.

Visualization of Local Structures in Quasi-One-Dimentional Halogen-Bridge Complexes[Ni_<1-x>Pd_x(chxn)_2Br]Br_2bySTM

准一维卤桥配合物[Ni_<1-x>Pd_x(chxn)_2Br]Br_2bySTM的局部结构可视化

• 发表时间: 2004
• 期刊: Angew.Chem.Int.Ed. 43
• 作者: Tomonori Nomoto;Taka-aki Ishibashi;Hiromi Okamoto;Hiro-o Hamaguchi;S.Takaishi et al.
• 通讯作者: S.Takaishi et al.

H.Tanaka et al.: "LESR Studies of Long-Lived Photogenerated Spins in the MX-Chain Complexes, Pd(chxn)_2Br_3"Synth.Met.. 135-136. 317-318 (2003)

H.Tanaka 等人：“MX 链复合物中长寿命光生自旋的 LESR 研究，Pd(chxn)_2Br_3”Synth.Met.. 135-136。

H.Miyasaka et al.: "Heterometallic Hexanuclear Cluster with and S=8 Spin Ground state : Mn^<II>{Mn^<II>(hfac)_2}_3[Ni^<II>(pao)_3]_2 Chfac^-=Hexafluoroacethylacetonate, pao^-=Pyridine-2-aldoxaimate)"Inorg.Chem.. 42. 4501 (2003)

H.Miyasaka 等人：“具有 S=8 自旋基态的异金属六核团簇：Mn^<II>{Mn^<II>(hfac)_2}_3[Ni^<II>(pao)_3]_2 Chfac