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

研究了剪切应力效应，以便将其引入有机材料和分子晶体的材料科学中。我们使用蓝宝石砧座，通过下砧在压力下旋转产生剪切应力，并在显微镜下进行原位观察和光谱测量。1.TMPD-TCNQ电荷转移盐的制备我们尝试了剪切变形的合成。在 TMPD N,N,N',N'-四甲基对苯二胺（无色）和 TCNQ（橙色）薄膜上施加剪切应力时，尖底外部的颜色变为蓝黑色。从拉曼光谱中可以看出，蓝黑色部分形成了TMPD-TCNQ CT盐。2.剪切应力对Pt(dpg)_2的影响，双(二苯基乙肟)铂(II)Pt(dpg)_2对应力敏感；它的颜色从红色变为绿色，再变为黄色。我们通过拉曼光谱研究了剪切应力效应。 1431和1452cm^-1处的C=N带由于剪切变形而显着移动。通过它们的波数变化来估计效果。通过旋转10°施加剪切应力后，中心部分的应力从0.14GPa增加到0.18GPa，外部部分的应力从1.77GPa强烈增加到2.41GPa。注意到剪切应力更多地施加在外部。3.剪切应力对螺吡喃6-硝基-BIPS的影响在剪切变形作用下，6-硝基-BIPS外部的颜色由橙色变为绿色。紫色的。由于荧光较强，绿色部分无法获得旋转振动拉曼光谱，而橙色和紫色部分却测量到了光谱。这一结果表明，剪切应力下的 ​​6-硝基-BIPS 分子与环境压力下的 6-硝基-BIPS 分子不同。

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.