Structurally and electronically modulated spin interaction of transient biradicals in two photon-gated stepwise photochromism†,Photochemical & Photobiological Sciences

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Structurally and electronically modulated spin interaction of transient biradicals in two photon-gated stepwise photochromism†
Photochemical & Photobiological Sciences ( IF 2.7 ) Pub Date : 2018-01-03 00:00:00 , DOI: 10.1039/c7pp00420f
Izumi Yonekawa _{1,

2,

3,

4,

5} , Katsuya Mutoh _{1,

2,

3,

4,

5} , Yoichi Kobayashi _{5,

6,

7,

8,

9} , Jiro Abe _{1,

2,

3,

4,

5}

Affiliation

The development of two-photon induced photochromic compounds is important for advanced photoresponsive materials. The utilization of the long-lived transient states or species for two-photon absorption is one of the efficient strategies to realize the advanced photochemical behavior beyond a one-photon photochemical reaction. We have synthesized bi-photochromic compounds composed of two photochromic phenoxyl-imidazolyl radical complex units. The biphotochromic compounds generate two biradical units when the two photochromic units absorb photons with a stepwise manner. The interaction between the two biradicals through the central bridging phenyl ring is the key feature to control the stepwise photochromic reaction. Here, we introduced aromatic spacers in order to modulate the distance and the dihedral angle between the biradical units. The color and the rate of the thermal back reaction of the stepwise photochromism can be regulated by the control of the central bridging part. These results give important insights to develop desirable advanced photoresponsive compounds.

中文翻译：

结构上和电子调节在双光子门控逐步光致变色瞬态双自由基的自旋相互作用†

双光子诱导的光致变色化合物的开发对于先进的光响应材料很重要。利用长寿命的瞬态或物种进行双光子吸收是实现超越单光子光化学反应的高级光化学行为的有效策略之一。我们已经合成了由两个光致变色苯氧基-咪唑基自由基复合单元组成的双光致变色化合物。当两个光致变色单元逐步吸收光子时，双光致变色化合物产生两个双自由基单元。通过中心桥联苯环的两个双自由基之间的相互作用是控制逐步光致变色反应的关键特征。在这里，我们引入了芳香族间隔基以调节双自由基单元之间的距离和二面角。逐步光致变色的颜色和热逆反应的速率可以通过中央桥接部分的控制来调节。这些结果为开发所需的先进光敏化合物提供了重要的见识。

更新日期：2018-01-03

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