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Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh4)2[Cu2I4].
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-04-01 , DOI: 10.1021/acs.inorgchem.0c00560 Yaouen Thefioux 1 , Marie Cordier 2 , Florian Massuyeau 1 , Camille Latouche 1 , Charlotte Martineau-Corcos 3, 4 , Sandrine Perruchas 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-04-01 , DOI: 10.1021/acs.inorgchem.0c00560 Yaouen Thefioux 1 , Marie Cordier 2 , Florian Massuyeau 1 , Camille Latouche 1 , Charlotte Martineau-Corcos 3, 4 , Sandrine Perruchas 1
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The photoluminescent stimuli-responsive properties of two crystalline polymorphs with the formula (PPh4)2[Cu2I4] are reported. Distinct luminescence properties are exhibited by these ionic copper iodide compounds with blue or yellow emission, and original luminescence thermochromism and mechanochromism are demonstrated. While one polymorph displays contrasted temperature-dependent emission properties, the other shows great modification of its emission upon mechanical solicitation. The establishment of structure-properties relationships, supported by a theoretical approach, permits us to get insights into the origin of the photoluminescence properties and the mechanisms at play. According to DFT calculations, the different emission bands originate either from the (PPh4)+ organic cation or from the [Cu2I4]2- anion. Activation of these two emissive centers appears to be dependent on the crystalline packing of the polymorph. The thermochromism displayed by one polymorph can be attributed to a variation in temperature of the relative intensities of two emission bands of two different excited states. The origin is different for the other polymorph, with emission bands coming from two independent emissive centers: namely, (PPh4)+ and [Cu2I4]2-. The luminescence mechanochromism is attributed to a polymorphic transition. The mechanical solicitation induces a partial transformation of one polymorph into the other within a disordered phase. The mechanochromic mechanism can be related to mechanical modifications of intermolecular interactions between the (PPh4)+ cations. By displaying luminescence properties that depend on crystalline structure, excitation wavelength, temperature, and mechanical solicitation, the studied copper iodides offer a great possibility of emissive color control and switching, a clear demonstration of the great potentialities of this family of compounds for the development of photoactive materials.
中文翻译：
多晶型碘化铜阴离子：（PPh4）2 [Cu2I4]的发光热致变色和机械变色。
报告了两种具有式（PPh4）2 [Cu2I4]的晶体多晶型物的光致发光响应特性。这些具有蓝色或黄色发射的离子型碘化铜化合物表现出不同的发光性质，并且证明了原始的发光热致变色和机械变色。一个多晶型物表现出对比的温度依赖性发射特性，而另一种多晶型物在机械诱导下表现出很大的发射变化。在理论方法的支持下，建立结构-性质关系，使我们能够洞悉光致发光性质的起源以及起作用的机理。根据DFT计算，不同的发射带源自（PPh4）+有机阳离子或[Cu2I4] 2-阴离子。这两个发射中心的激活似乎取决于多晶型物的晶体堆积。一个多晶型物显示的热致变色可归因于两个不同激发态的两个发射带的相对强度的温度变化。其他多晶型物的起源不同，其发射带来自两个独立的发射中心：（PPh4）+和[Cu2I4] 2-。发光机械致变色归因于多晶型转变。机械诱导在无序相内引起一个多晶型物向另一种多晶型物的部分转化。机械变色机理可能与（PPh4）+阳离子之间的分子间相互作用的机械修饰有关。通过显示取决于晶体结构，激发波长的发光特性，
更新日期：2020-04-24
中文翻译：
多晶型碘化铜阴离子：（PPh4）2 [Cu2I4]的发光热致变色和机械变色。
报告了两种具有式（PPh4）2 [Cu2I4]的晶体多晶型物的光致发光响应特性。这些具有蓝色或黄色发射的离子型碘化铜化合物表现出不同的发光性质，并且证明了原始的发光热致变色和机械变色。一个多晶型物表现出对比的温度依赖性发射特性，而另一种多晶型物在机械诱导下表现出很大的发射变化。在理论方法的支持下，建立结构-性质关系，使我们能够洞悉光致发光性质的起源以及起作用的机理。根据DFT计算，不同的发射带源自（PPh4）+有机阳离子或[Cu2I4] 2-阴离子。这两个发射中心的激活似乎取决于多晶型物的晶体堆积。一个多晶型物显示的热致变色可归因于两个不同激发态的两个发射带的相对强度的温度变化。其他多晶型物的起源不同，其发射带来自两个独立的发射中心：（PPh4）+和[Cu2I4] 2-。发光机械致变色归因于多晶型转变。机械诱导在无序相内引起一个多晶型物向另一种多晶型物的部分转化。机械变色机理可能与（PPh4）+阳离子之间的分子间相互作用的机械修饰有关。通过显示取决于晶体结构，激发波长的发光特性，
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