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Preferential Solvation Unveiled by Anomalous Conformational Equilibration of Porphyrin Dimers: Nucleation Growth of Solvent–Solvent Segregation
The Journal of Physical Chemistry B ( IF 2.8 ) Pub Date : 2018-05-01 00:00:00 , DOI: 10.1021/acs.jpcb.8b02558
Mitsuhiko Morisue 1 , Ikuya Ueno 1
The Journal of Physical Chemistry B ( IF 2.8 ) Pub Date : 2018-05-01 00:00:00 , DOI: 10.1021/acs.jpcb.8b02558
Mitsuhiko Morisue 1 , Ikuya Ueno 1
Affiliation
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Preferential solvation was explored using ethynylene- or butadiynylene-linked porphyrin dimers bearing 3,4,5-tri((S)-3,7-dimethyloctyloxy)phenyl groups at the meso positions in binary hexafluorobenzene (C6F6) and cyclohexane (C6H12) mixture, expecting contrasting solvent affinity of the porphyrin core and the alkyl side chains toward the individual solvent component. Although the solvent polarity remained nearly constant along with the continuous variation of the solvent composition, the porphyrin dimer showed dramatic change in spectroscopic signatures, indicating the occurrence of preferential solvation. Because of small rotational barrier around the ethynylene and butadiynylene linkage, the torsional conformations of the porphyrin dimers varied from orthogonal to planar due to continuous variation of molar fraction of C6H12–C6F6 mixture. Thorough thermodynamic analyses inferred that nucleation as the enthalpic component and phase segregation as the entropic component operated preferential solvation. The porphyrin dimer nucleated the C6H12–C6F6 segregation, and the torsional conformation was diagnostic of the inversion of the interfacial curvature of the solvent segregation along with the continuous variation.
中文翻译：
卟啉二聚体异常构象平衡揭示的优先溶剂化：溶剂-溶剂偏析的成核生长
探索了使用二乙六氟苯（C 6 F 6）的内消旋位置带有3,4,5-三（（S）-3,7-二甲基辛氧基氧基）苯基的乙炔基或丁二炔基连接的卟啉二聚体的优先溶剂化方法C 6高12）混合物，期望卟啉核心和烷基侧链对单个溶剂组分的溶剂亲和力相反。尽管随着溶剂组成的连续变化，溶剂极性几乎保持恒定，但卟啉二聚体在光谱特征上显示出戏剧性的变化，表明发生了优先的溶剂化。由于乙炔和丁二炔键周围的旋转势垒较小，由于C 6 H 12 –C 6 F 6摩尔分数的连续变化，卟啉二聚体的扭转构象从正交变化为平面混合物。彻底的热力学分析表明，成核是焓组分，相分离是熵组分，它们优先发生溶剂化作用。卟啉二聚体使C 6 H 12 –C 6 F 6偏析成核，并且扭转构象可以诊断溶剂偏析的界面曲率随连续变化而反转。
更新日期：2018-05-01
中文翻译：
卟啉二聚体异常构象平衡揭示的优先溶剂化：溶剂-溶剂偏析的成核生长
探索了使用二乙六氟苯（C 6 F 6）的内消旋位置带有3,4,5-三（（S）-3,7-二甲基辛氧基氧基）苯基的乙炔基或丁二炔基连接的卟啉二聚体的优先溶剂化方法C 6高12）混合物，期望卟啉核心和烷基侧链对单个溶剂组分的溶剂亲和力相反。尽管随着溶剂组成的连续变化，溶剂极性几乎保持恒定，但卟啉二聚体在光谱特征上显示出戏剧性的变化，表明发生了优先的溶剂化。由于乙炔和丁二炔键周围的旋转势垒较小，由于C 6 H 12 –C 6 F 6摩尔分数的连续变化，卟啉二聚体的扭转构象从正交变化为平面混合物。彻底的热力学分析表明，成核是焓组分，相分离是熵组分，它们优先发生溶剂化作用。卟啉二聚体使C 6 H 12 –C 6 F 6偏析成核，并且扭转构象可以诊断溶剂偏析的界面曲率随连续变化而反转。
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