Shear stress effect on molecular crystals and development of their new synthetic methods

剪切应力对分子晶体的影响及其新合成方法的开发

• 批准号: 15550134
• 负责人: INOKUCHI Makoto
• 金额: $ 1.92万
• 依托单位: Tokyo University of Science, Yamaguchi
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550134/
• 关键词: shear stress; high pressure; molecular crystal; Raman spectroscopy; chromism; charge transfer salt; bis(glyoximato) platinum complex; spiropyran; shear stress; DAC; 金属グリオキシマート錯体; 白金グリオキシマート錯体; TMPD-TCNQ

The shear stress effect has been studied in order to introduce it to materials science for organic materials and molecular crystals. We have used the sapphire anvil cell to generate shear stress by the rotation of the lower anvil under pressure and performed the in situ observations under a microscope with spectroscopic measurements.1.Preparation of TMPD-TCNQ charge-transfer saltWe have attempted the syntheses by shear deformation. On applying the shear stress on TMPD N,N,N',N'-tetramethyl-p-phenylenediamine, colorless) and TCNQ (orange) films, the color at the outer part on the culet changed to blue-black. From the Raman spectra, the formation of TMPD-TCNQ CT salt at the blue-black part was confirmed.2.Shear stress effect on Pt(dpg)_2, bis(diphenylglyoximato) platinum(II)Pt(dpg)_2 is sensitive to the stress ; its color changes from red to green to yellow. We have studied the shear stress effect by Raman spectroscopy. The C=N bands at 1431 and 1452 cm^<-1> were shifted significantly by the shear deformation. The estimation of the effect was performed by their shifts in wavenumber. On applying the shear stress by the rotation of 10゜, the stress was increased from 0.14 GPa to 0.18 GPa at the center part and from 1.77 GPa to 2.41 GPa at the outer part. It was noted that the shear stress was applied more strongly at the outer part.3.Shear stress effect on Spiropyran 6-nitro-BIPSThe color of 6-nitro-BIPS at the outer part was changed from orange to green under shear deformation. As being released from the stress, it changed from green to purple. Because of strong fluorescence, the rotation-vibration Raman spectrum could not be obtained at the green part, while the spectra were measured at the orange and purple parts. This result suggests that 6-nitro-BIPS molecule under shear stress is different from one at ambient pressure.

为了将剪应力效应引入到有机材料和分子晶体的材料科学中，对剪应力效应进行了研究。我们利用蓝宝石砧座在压力下旋转下砧座产生剪应力，并在显微镜下进行了原位观察，并进行了光谱测量。1.TMPD-TCNQ电荷转移盐的制备我们尝试了剪切变形合成。在TMPD，N，N，N‘，N’-四甲基对苯二胺(无色)和TCNQ(橙色)薄膜上施加剪切力，花冠外部的颜色变为蓝黑色。从拉曼光谱可以看出，TMPD-TCNQ CT盐的形成位于蓝黑色部分。2.铂(DPG)_2、双(二苯基乙二酮亚胺)铂(II)、铂(DPG)_2的剪应力效应对应力很敏感，颜色由红变绿变黄。我们用拉曼光谱研究了切应力效应。剪切变形使1431和1452 cm^&lt；-1&gt；处的C=N带明显移动。通过它们的波数变化来估计其影响。当旋转10゜施加剪应力时，中央应力从0.14 GPA增加到0.18 GPA，外部从1.77 GPA增加到2.41 GPA。3.剪切应力对螺吡喃6-硝基-联苯并吡喃的影响6-硝基-联苯并[6-硝基]-联苯并[6-硝基]-联苯并[6-硝基]-联苯并[6-硝基]-联苯并[6-硝基]-联苯并(6-硝基)-联苯并[6-硝基]-联苯并(6-硝基)-联苯并(6-硝基-联苯)酮在剪切变形下，其外层颜色由橙色变为绿色。随着压力的释放，它从绿色变成了紫色。由于荧光强，在绿色部分无法获得旋转振动拉曼光谱，而在橙色和紫色部分测量到了光谱。这一结果表明，剪切力作用下的6-硝基-BIPS分子不同于常压下的6-硝基-BIPS。

项目成果

I.Shirotani, H.Hayashi, K.Hirano, H.Kawamura, M.Inokuchi, K.Yakushi.H.Inokuchi: "Shear stress effects on electronic spectra on the one-dimensional bis(diphenyl glyoximato)metal(II) complexes, M(dpg)_2 [M= Ni and Pt] under high pressure"Proceedings of the

I.Shirotani、H.Hayashi、K.Hirano、H.Kawamura、M.Inokuchi、K.Yakushi.H.Inokuchi：“剪切应力对一维双（二苯基乙肟）金属（II）配合物电子光谱的影响

Shear stress effect on thin films of platinum complex Pt(dpg)_2 and chromic compounds

铂络合物Pt(dpg)_2和铬化合物薄膜的剪切应力效应

• 期刊: Journal of Low Temperature Physics (in press)
• 作者: I.Shirotani;H.Hayashi;K.Hirano;H.Kawamura;M.Inokuchi;K.Yakushi;H.Inokuchi;Y.Uemichi;M.Inokuchi et al.
• 通讯作者: M.Inokuchi et al.

Raman Spectroscopic Study of bis(diphenylglyoximato) metal complexes under high pressure

高压下双(二苯基乙肟)金属配合物的拉曼光谱研究

• 期刊: Molecular Crystal and Liquid Crystal (in press)
• 作者: I.Shirotani;H.Hayashi;K.Hirano;H.Kawamura;M.Inokuchi;K.Yakushi;H.Inokuchi;Y.Uemichi;M.Inokuchi et al.;上道芳夫;K.Yabuuchi et al.
• 通讯作者: K.Yabuuchi et al.

Shear stress effects on electronic spectra on the one-dimensional bis(diphenylglyoximato)metal(II) complexes, M(dpg)_2 [M=Ni and Pt] under high pressure

高压下剪切应力对一维双(二苯基乙肟)金属(II)配合物M(dpg)_2 [M=Ni 和 Pt] 电子谱的影响

• 发表时间: 2003
• 期刊: Proceedings of the Japan Academy, SeriesB Vol.79
• 作者: I.Shirotani;H.Hayashi;K.Hirano;H.Kawamura;M.Inokuchi;K.Yakushi;H.Inokuchi
• 通讯作者: H.Inokuchi

Shear stress effects on electronic spectra on the one-dimensional bis(diphenylglyoximato)metal(II) complexes, M(dpg)_2[M=Ni and Pt]under high pressure

高压下剪切应力对一维双(二苯基乙肟)金属(II)配合物M(dpg)_2[M=Ni and Pt]电子谱的影响

• 发表时间: 2003
• 期刊: Proceedings of the Japan Academy SeriesB,79
• 作者: M.Inokuchi;A.Nagaoka;M.Yamamoto;I.Shirotani;J.Hayashi;K.Yakushi;H.Kawamura;H.Inokuchi;Y.Uemichi;I.Shirotani et al.
• 通讯作者: I.Shirotani et al.