RESUMEN
Invited for the cover of this issue are the groups of Kazuteru Usui and Satoru Karasawa at Showa Pharmaceutical University and Yasuhiro Kobori of Kobe University. The image depicts chirality control of helical compounds through cycles of photocleavage and recombination under sunlight with a "Jack and the Beanstalk" motif. Read the full text of the article at 10.1002/chem.202302413.
RESUMEN
Herein, we report the synthesis of two "partially embedded fused-dihydropyridazine N-aryl aza[5]helicene derivatives" (PDHs) and the demonstration of their intrinsic photo-triggered multi-functional properties based on a Kekulé biradical structure. Introducing bulky electron-withdrawing trifluoromethyl or pentafluoroethyl groups into the aza[5]helicene framework (PDH-CF3 and -C2 F5 ) gives PDH axial chirality based on the helicity of the P and M forms, even at room temperature. Upon photo-irradiation of PDH-CF3 in a frozen solution, an ESR signal from the triplet biradical with zero-field splitting values, generated by N-N bond dissociation, was observed. However, when the irradiation was turned off, the ESR signal became silent, thus indicating the existence of two equilibria: between the biradical and quinoidal forms based on the Kekulé structure, and between N-N bond cleavage and recombination. The observed photo- and thermally induced behaviors indicate that T-type photochromic molecules are involved in the photoisomerization mechanism involving the two equilibria. Inspired by the photoisomerization, chirality control of PDH by photoracemization was achieved. Multiple functionalities, such as T-type photochromism, photo-excitation-mediated triplet biradical formation, and photoracemization, which are attributed to the "partially embedded dihydropyridazine" structure, are demonstrated.
RESUMEN
We show that both the optical stopband wavelength and effective bandwidth of films of gel-immobilized loosely packed colloidal photonic crystals can be controlled over a wide range. When the gelation reagent of the charge-stabilized colloidal crystals was photopolymerized under ultraviolet light using different upper- and bottom-light intensities, it resulted in a gel-immobilized colloidal crystal film with a broadened Bragg reflection peak. Moreover, the width of the Bragg peak increased from 30 to 190 nm as the difference between the light intensities increased. Films with wider Bragg peaks exhibited a brighter reflection color because of the superposition of the shifted Bragg reflections. Furthermore, the Bragg wavelength could be varied over a wide range (500-650 nm) while maintaining the same broadened effective bandwidth by varying the swelling solvent concentration. These findings will expand the applicability of colloidal crystals for use in photonic devices and color pigments.