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机械研磨时铂(II)配合物固体的发光颜色变化。

Luminescence color change of a platinum(II) complex solid upon mechanical grinding.

作者信息

Abe Taichi, Itakura Toru, Ikeda Noriaki, Shinozaki Kazuteru

机构信息

Department of Chemistry Graduate School of Integrated Sciences, Yokohama City University, 22-2 Seto, Yokohama, 236-0027, Japan.

出版信息

Dalton Trans. 2009 Jan 28(4):711-5. doi: 10.1039/b811107c.

Abstract

The mechanochemical behavior of Pt(5dpb)Cl (5dpbH = 1,3-di(5-methyl-2-pyridyl)benzene) was investigated in terms of solid-state luminescence. The yellow luminescence of the crystalline complex changed to orange when grinding into fine powder on a glass substrate with a spatula. A broad emission band, which was not detected for the crystal, was observed at around 670 nm for the powder. The powder X-ray diffraction (XRD) pattern was the same as that calculated from X-ray crystallographic data of the single crystal. A broad band appeared within 100 ns after laser excitation accompanied by quenching of the s(pi,pi*) emission of Pt(5dpb)Cl, which was then weakened with decreasing temperature and disappeared below 120 K. The phenomenon was very similar to the excimer formation observed in solution. A related complex, Pt(dpb)Cl (dpbH = 1,3-di(2-pyridyl)benzene), also exhibited luminescent mechanochromism. However, the broad emission that appeared upon grinding still remained at 77 K, and XRD showed that the ground sample of Pt(dpb)Cl was amorphous.

摘要

从固态发光的角度研究了Pt(5dpb)Cl(5dpbH = 1,3 - 二(5 - 甲基 - 2 - 吡啶基)苯)的机械化学行为。当用刮刀在玻璃基板上研磨成细粉时,结晶配合物的黄色发光变为橙色。对于粉末,在670 nm左右观察到一个晶体中未检测到的宽发射带。粉末X射线衍射(XRD)图谱与从单晶的X射线晶体学数据计算得到的图谱相同。激光激发后100 ns内出现一个宽带,同时Pt(5dpb)Cl的s(π,π*)发射猝灭,随后随着温度降低该宽带减弱,在120 K以下消失。该现象与溶液中观察到的准分子形成非常相似。一种相关配合物Pt(dpb)Cl(dpbH = 1,3 - 二(2 - 吡啶基)苯)也表现出发光机械变色现象。然而,研磨后出现的宽发射在77 K时仍然存在,并且XRD显示Pt(dpb)Cl的研磨样品是无定形的。

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