Two novel photochromic naphthopyrans containing naphthalimide moieties (Nip1 and Nip2) were studied in solution under flash photolysis conditions, exhibiting highly photochromic response, rapid thermal bleaching rate and good fatigue-resistance. Owing to the different N-substituted imide groups at the naphthalimide units, the thermal bleaching rate of Nip2 bearing phenyl on the naphthalimide unit is found to be approximately 2 times that of Nip1 bearing n-butyl, indicating that the photochromic properties can be modulated with introduction of different functional groups on the naphthalimide unit. In Nip1 and Nip2, the strong electron-withdrawing effect of the imide group incorporated at the naphthalimide moiety maintains several merits: (i) shifting absorption bands to longer wavelength, (ii) beneficial to an enhancement in the ratio of transoid-cis (TC) isomer and an increase in the transformation rate from transoid-trans (TT) to TC with respect to reference compound NP, and (iii) resulting in a preferable color bleaching rate and fading absolutely to their colorless state with thermal reversibility. As demonstrated in the system of NP, the slow transformation process from TT to TC might be the predominant dynamic step in thermal back process, leading to the residual color of NP being only faded to its original colorless state by visible light irradiation. The optical densities of colored forms for Nip1 and Nip2 are dependent upon the intensity of incident light, ensuring a possible application in the manufacture of ophthalmic lenses and smart windows. Moreover, the fluorescence of Nip1 and Nip2 can be switched on and off by photoinduced conversion between the closed and open forms.

A new photochromic bisthienylethene system (BTE-NAFc) is reported in which the ferrocene unit (Fc) is incorporated into a naphthalimide chromophore as the central ethene bridging unit. The incorporated Fc unit in the photochromic system of BTE-NAFc has several effects on optical properties, such as fluorescence-modulation through photoinduced electron transfer (PET), a decrease in the photochromic cyclization quantum yield, and a selective two-step oxidation process. The ability to drive ring-opening and ring-closing reactions with a secondary redox-modulation provides increased functionality to the photochromic system. Based on these meaningful photo- and redox-modulation properties, five unprecedented multi-addressable states (BTE-NAFc, BTE-NAFc(+), c-BTE-NAFc, c-BTE-NAFc(+), and BTE(+)-NAFc(+)) and gated photochromism are successfully obtained within the unimolecular BTE platform, thus providing deeper insight into photochromic systems as multifunctional outputs.

A diarylethene molecule consisting of an 1,8-naphthalic anhydride and two 2,5 dimethylthiophene which exhibits reversible fluorescence switching capacity as well as solvatochromism with red shift of the fluorescence maximum by more than 150 nm.