Insights into Proton Dynamics in a Photofunctional Salt‐Cocrystal Continuum: Single‐Crystal X‐ray, Neutron Diffraction, and Hirshfeld Atom Refinement
Insights into Proton Dynamics in a Photofunctional Salt‐Cocrystal Continuum: Single‐Crystal X‐ray, Neutron Diffraction, and Hirshfeld Atom Refinement
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深入了解光功能盐共晶连续体中的质子动力学：单晶 X 射线、中子衍射和赫什菲尔德原子细化
DOI：
10.1002/chem.202103044
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Yoshio Hisaeda
中科院分区：
文献类型：
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作者：
Yoshio Yano;Toshikazu Ono;Takashi Ohhara;Yoshio Hisaeda
用X射线衍射法、中子衍射法和理论计算研究了酸碱配合物的光学性质与质子化程度的关系。我们用吡啶修饰的吡咯衍生物和水杨酸合成了五种酸碱配合物。所制备的酸碱络合物中有两种是无客体晶体的晶型，发出绿色光；另外三种是含有CH2Cl2、CH2Br2或C2H4Cl2的客体包裹体晶体。客体的存在或不存在导致发射改变颜色，改变了酸碱络合物之间的氢键强度。在123至273⋅⋅⋅K温度范围内，吡啶部分和羧基之间的准确N H距离对于无客体晶体为1.40 ä，对于客体包裹体晶体为1.25 ä。我们的发现有助于更好地理解酸碱络合物中光功能和质子动力学之间的复杂关系。
X‐ray diffraction, neutron diffraction, and theoretical calculations were used to investigate the relationship between the optical properties and degree of protonation in acid‐base complexes. We prepared five acid‐base complexes by using a pyridine‐modified pyrrolopyrrole derivative and salicylic acid. Two of the prepared acid‐base complexes were polymorphs of guest‐free crystals with green emission; the other three were guest‐inclusion crystals with yellow emission containing CH2Cl2, CH2Br2, or C2H4Cl2. The presence or absence of guests caused the emission to change color, altering the hydrogen bond strength between the acid‐base complexes. Accurate N⋅⋅⋅H distances between the pyridyl moiety and the carboxy group over the temperature range 123 to 273 K were 1.40 Å for the guest‐free crystals and 1.25 Å for the guest‐inclusion crystals. Our findings contribute to a better understanding of the complex relationship between photofunction and proton dynamics in acid‐base complexes.