Single-Crystal-to-Single-Crystal [2 + 2] Photocycloaddition Reaction in a Photosalient One-Dimensional Coordination Polymer of Pb(II),Journal of the American Chemical Society

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Single-Crystal-to-Single-Crystal [2 + 2] Photocycloaddition Reaction in a Photosalient One-Dimensional Coordination Polymer of Pb(II)
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-11-11 , DOI: 10.1021/jacs.0c09577
Bibhuti Bhusan Rath ₁ , Jagadese J. Vittal ₁

Affiliation

In a remarkable example, we report a one-dimensional coordination polymer (CP) of Pb(II) showing photosalient (PS) properties triggered by [2 + 2] cycloaddition of olefinic ligands, which is seldom observed in CPs. Macroscopic rod-shaped crystals show various photomechanical effects such as jumping, splitting, rolling, and breaking upon UV illumination. In this rare example, we could determine the solid-state structure of the 100% dimerized product and three intermediate structures, even after the shattering of crystals into small pieces. Detailed mechanistic investigation from the single-crystal data indicates that the strain generated in the unit cell due to anisotropic expansion played a bigger role for the PS effects. Nucleated growth of the photoproduct crystal created different domains inside the single crystal, which multiplied the already developed stress leading to the photomechanical movements. This example falls in the gray area of a clean single-crystal-to-single-crystal (SCSC) transformation and violent PS effect. Such photochemical behavior has never been reported before.

中文翻译：

单晶到单晶 [2 + 2] 光致显着 Pb(II) 一维配位聚合物中的光环加成反应

在一个显着的例子中，我们报告了 Pb(II) 的一维配位聚合物 (CP)，显示出由烯烃配体的 [2 + 2] 环加成引发的光显着 (PS) 特性，这在 CP 中很少观察到。宏观棒状晶体在紫外线照射下表现出各种光机械效应，如跳跃、分裂、滚动和断裂。在这个罕见的例子中，我们可以确定 100% 二聚产物的固态结构和三个中间结构，即使在晶体破碎成小块之后也是如此。单晶数据的详细机理研究表明，由于各向异性膨胀在晶胞中产生的应变对 PS 效应起着更大的作用。光产物晶体的成核生长在单晶内部产生了不同的域，这将导致光机械运动的已经形成的应力成倍增加。这个例子属于干净的单晶到单晶 (SCSC) 转换和剧烈 PS 效果的灰色区域。以前从未报道过这种光化学行为。

更新日期：2020-11-11

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