Synthesis and Functions of Binaphthyl Derivatives with Comprehensive Introduction of Phenylethynyl Groups

In this study, compounds with phenylethynyl (PE) groups introduced at all of the possible positions of the methylene-bridged structure of the 1,1ʹ-bi-2-naphthol backbone (3-PE to 8-PE) were synthesized. Compounds with four or six phenylethynyl groups (3,6-PE, 4,6-PE, 5,6-PE, 6,7-PE, and 3,4,6-PE) were also synthesized. The key reaction for the synthesis of these compounds was the Sonogashira reaction using halogen scaffolds. The new transformation methods include (1) selective bromination of the 5-position of the binaphthyl skeleton and (2) bromination of the 6-position and then iodination of the 4-position, followed by the Sonogashira reaction of iodine at the 4-position and lithiation and protonation of bromine at the 6-position. The optical properties of the compounds were evaluated. The extension of the π system greatly differed depending on the position of the phenylethynyl group. 4-PE, 4,6-PE, and 3,4,6-PE, in which the phenylethynyl groups were introduced in the extended direction of the naphthalene linkage axis, showed longer absorption and emission wavelengths and higher fluorescence quantum yields than the other compounds. In circularly polarized luminescence measurements, 7-PE showed a relatively large glum value, an interesting finding that reverses the sense.