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Structures and Oxidation Properties of Phenylene-Bridged Diazacycloalkanes: Ring Size Effects on Structures and Properties
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2022-08-10 , DOI: 10.1021/acs.joc.2c01174 Wataru Setaka 1 , Kazuki Kajiyama 1 , Yusuke Inagaki 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2022-08-10 , DOI: 10.1021/acs.joc.2c01174 Wataru Setaka 1 , Kazuki Kajiyama 1 , Yusuke Inagaki 1
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Phenylenediamine derivatives have been investigated as functional molecules because of their characteristic oxidation properties. In this study, phenylene-bridged diazacycloalkanes, that is, C10, C12, and C14, in which numbers indicate the lengths of a side chain, were synthesized, and the effects of the macroring size on their structures and oxidation properties were investigated. X-ray crystallography revealed that the structures around the nitrogen atoms were remarkably dependent on the chain lengths. The benzene plane of C10 is arranged almost perpendicular to the macroring to avoid steric contact. However, the benzene plane of C14 and alkyl frame were co-planar. Stabilization resulting from conjugation was comparable to destabilization caused by macroring strain according to DFT calculations. Structural differences between C10 and C14 caused changes in the NMR chemical shifts of the inner methylene protons and first oxidation potentials in solution. Notably, the properties of C12 can be analyzed as those of distributed structures, which is of interest with respect to exploiting the metastable structure of the molecules. The observed relationships between the steric structures and properties can facilitate the design of functional molecules containing phenylenediamine moieties.
中文翻译：
亚苯基桥连二氮杂环烷的结构和氧化性质：环尺寸对结构和性质的影响
苯二胺衍生物因其特有的氧化特性而被作为功能分子进行了研究。本研究合成了以数字表示侧链长度的亚苯基桥连二氮杂环烷烃，即C10、C12和C14 ，并研究了大环尺寸对其结构和氧化性能的影响。X 射线晶体学显示氮原子周围的结构显着依赖于链长。C10的苯平面几乎垂直于大环排列以避免空间接触。然而，C14的苯平面和烷基框架是共面的。根据 DFT 计算，共轭引起的稳定与宏环应变引起的不稳定相当。C10和C14之间的结构差异导致内部亚甲基质子的 NMR 化学位移和溶液中的第一氧化电位发生变化。值得注意的是，C12的特性可以分析为分布式结构的特性，这对于利用分子的亚稳态结构很有意义。观察到的空间结构和性质之间的关系可以促进含有苯二胺部分的功能分子的设计。
更新日期：2022-08-10
中文翻译：
亚苯基桥连二氮杂环烷的结构和氧化性质：环尺寸对结构和性质的影响
苯二胺衍生物因其特有的氧化特性而被作为功能分子进行了研究。本研究合成了以数字表示侧链长度的亚苯基桥连二氮杂环烷烃，即C10、C12和C14 ，并研究了大环尺寸对其结构和氧化性能的影响。X 射线晶体学显示氮原子周围的结构显着依赖于链长。C10的苯平面几乎垂直于大环排列以避免空间接触。然而，C14的苯平面和烷基框架是共面的。根据 DFT 计算，共轭引起的稳定与宏环应变引起的不稳定相当。C10和C14之间的结构差异导致内部亚甲基质子的 NMR 化学位移和溶液中的第一氧化电位发生变化。值得注意的是，C12的特性可以分析为分布式结构的特性，这对于利用分子的亚稳态结构很有意义。观察到的空间结构和性质之间的关系可以促进含有苯二胺部分的功能分子的设计。
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