Turn-On Mode Fluorescence Switch by Using Negative Photochromic

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Turn-On Mode Fluorescence Switch by Using Negative Photochromic Imidazole Dimer Katsuya Mutoh, Nanae Miyashita, Kaho Arai, and Jiro Abe J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 19 Mar 2019 Downloaded from http://pubs.acs.org on March 19, 2019

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Turn-On Mode Fluorescence Switch by Using Negative Photochromic Imidazole Dimer Katsuya Mutoh, Nanae Miyashita, Kaho Arai, and Jiro Abe* Department of Chemistry, School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan

Supporting Information Placeholder ABSTRACT: The development of fluorescence switchable molecules in several polar and apolar environments has been required for fluorescence imaging of nanostructures. Photochromic molecules are an important class for the reversible light-triggered fluorescence switching. Although many studies of fluorescence switching by using photochromic reactions have been reported, the report of photochromic molecules reversibly showing turn-on mode fluorescence switching has been limited in spite of their importance. Herein, we report the photoactivatable fluorescence based on negative photochromism, where the absorption spectrum of the compound after irradiation is blue-shifted relative to that before irradiation. We introduced naphthalimide units as a green fluorophore to the negative photochromic binaphthyl-bridged imidazole dimer. The fluorescence of the naphthalimide unit is efficiently quenched in the initial colored isomer (fluorescence quantum yield: Φfluo. = 0.01) by Förster resonance energy transfer. In contrast, the fluorescence quantum yield increases up to 0.75 in the transient isomer formed by the negative photochromic reaction. The fluorescence intensity thermally decreases with the thermal back reaction to form the original stable colored form. These results indicate that the negative photochromic molecules are suitable for turn-on mode fluorescence switches and will give an attractive insight for the development of reversible fluorescence switching molecules.

Fluorescence switchable molecules are of interest because of the potentially applicable feature to fluorescence imaging including super resolution imaging, single molecule tracking and fluorescent sensors.1–6 Among the fluorescence switches, the reversibly photoswitchable fluorescent dyes by using photochromic molecules have been frequently studied and reported.7–18 The most of them are turn-off mode fluorescence switches in which the initial colorless state is fluorescent while the metastable colored state generated by the photoisomerization is non-fluorescent because of the fluorescence quenching by an energy or an electron transfer.8–13 The turn-off mode fluorescence switching can be applied to RESOLFT type super resolution microscopy and optical memory media. In contrast, the development of turn-on mode fluorescence switchable molecules is also required because it has an advantage that the fluorescence from single molecule can be detected under a dark background and can be applicable to super resolution imaging by using photoactivated localization microscopy (PALM)/stochastic optical reconstruction microscopy (STORM) techniques.14–18 Recently, some studies about the turn-on mode switching have been reported by Irie and Raymo.14–20 They have used photoactivatable fluorescent diarylethenes or spirooxazine derivatives and succeeded to

Scheme 1. Fluorescence Switches by Using (a) Photochromic Imidazole Dimer and (b) Negative Photochromic Imidazole Dimer (1 and 2).

construct super resolution images.17,19 These results have led to an increasing demand for the organic molecular design to reversibly photoactivate fluorescence. Negative photochromism has been well known as the reversible color change from colored to colorless upon visible light irradiation. Because the absorption bands of the stable colored state in visible light region disappear upon visible light irradiation, negative photochromism has several advantages over conventional photochromism such as (i) a high efficiency of the reaction inside of materials and (ii) no requirement of UV light as an excitation light source which damages materials and cells. Therefore, the negative photochromic molecule is an attractive molecular switch not only for functional materials but also for biological activities. Furthermore, it is suitable for turn-on mode fluorescence switching because the photo-induced bleaching of the absorption in visible light region can lead to the enhancement of fluorescence intensity by carefully selecting the photochromophores and fluorophores to satisfy the energy matching condition. However, the efficient photoactivation



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Figure 1. Absorption spectra of 1-O, 1-Y, 2-O and 2-Y in benzene.

Figure 3 Absorption, fluorescence and excitation spectra of 1-O, 1-Y, 2-O and 2-Y (2.9×10−6 M) in benzene. Table 1 Fluorescence Quantum Yields (Φfluo.) of 1 and 2. Figure 2 Thermal recovery processes of the absorption spectra after visible light (400–700 nm, 260 mW) irradiation to (a, b) 1 (2.0×10−5 M) and (c, d) 2 (2.0×10−5 M) in benzene at 298 K.

and reversible switching of fluorescence by using negative photochromism have been limited to date21 even though the development of attractive negative photochromic molecules has recently gained much attention.22–31 One of the reasons about the limited report of the applications of negative photochromic molecules are the strong dependence of the reaction efficiency on the environment.21,26,32–40 In this study, we demonstrated the turn-on mode fluorescence switch by the combination of a negative photochromic binaphthylbridged imidazole dimer (BN-ImD)28 and 4-(N,N’-dimethylamino)-1,8-naphthalimide as a fluorophore. We have recently succeeded to develop the turn-off mode fluorescence switch by using photochromic imidazole dimers (Scheme 1a).41–43 Because the initial colorless form of the imidazole dimer generates the colored biradical having broad absorption bands in the visible light region, the fluorescence of the incorporated fluorophore can be efficiently quenched in the transient colored biradical state. On the other hand, the initial orange-colored form of BN-ImD possessing an absorption band at 500 nm photochemically isomerizes to the metastable colorless form upon visible light irradiation. The colorless form returns to the colored form thermally. The advantage of the negative photochromism of BN-ImD is the efficient switching ability which is unselective against the polarity of environment. 4-Amino-1,8naphthalimide is a well-known fluorophore emitting green fluorescence with high fluorescence quantum yield (Φfluo. = ca. 0.8).44–47 Because the absorption spectrum of the colored form of BN-ImD shows large overlap with the fluorescence spectrum of naphthalimide, the efficient fluorescence quenching by Förster resonance energy transfer (FRET) can be expected in the colored form. We designed and synthesized two BN-ImD derivatives, 1 and 2,

Φfluo.

1-O

1-Y

2-O

2-Y

0.01

0.75

0.01

0.71

indirectly and directly connected with naphthalimide units, respectively. The orange forms of 1 and 2 (1-O and 2-O) have a similar absorption band at 500 nm with that of BN-ImD as shown in Figure 1. This suggests that the BN-ImD units and the naphthalimide units are not conjugated, and therefore, the phenyl ring at the 4 and 5position of the imidazole and the naphthalimide units of 2 would be almost perpendicular because of the large steric hindrance of the carbonyl groups. Upon visible light irradiation, the absorption band at 500 nm disappeared and the solutions of 1-O and 2-O changed the color from orange to yellow accompanying with the isomerization from 1-O and 2-O to the yellow forms of 1 and 2 (1-Y and 2Y), respectively. The absorption bands at 400 nm of 1-Y and 2-Y are the characteristic band originated from the naphthalimide units. Figure 2 shows the spectral changes in association with the thermal back reactions from the yellow to the orange forms in benzene at 298 K. The absorbance at 500 nm monotonically recovers after ceasing the excitation visible light, and the half-lives of 1-Y and 2Y were estimated to be 110 s and 48 s at 298 K, respectively. The conversion efficiencies from the orange to the yellow forms of 1 and 2 in benzene were estimated to be 0.07 and 0.19, respectively (supporting information).28 The activation energy barriers and parameters were estimated from the Eyring plots and summarized in Table S5. While the thermal back reaction rate of 1-Y is almost identical to that of the colorless form of BN-ImD, that of 2-Y is two times larger. It is presumably because the sterically large framework of the naphthalimide unit destabilizes 2-Y, resulting in the acceleration of the thermal back reaction.48


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We demonstrated the photoactivation of the fluorescence for 1 and 2 by the negative photochromism as shown in Figure 3 and Table 1. The excitation spectra of 1 and 2 have only the absorption band at 400 nm. In addition, no spectral shift of the fluorescence of 1 and 2 was observed, compared with the fluorescence spectrum of 4-dimethylamino-1,8-naphthalimide (Figure S41), indicating that the excited state of the BN-ImD is not related to the radiative relaxation process. The absorption spectra of the orange forms and the fluorescence spectra of the naphthalimide units show the efficient overlap, and therefore, the orange forms emit very weak fluorescence in benzene at 298 K. In contrast, the fluorescence intensity drastically increases after the photoisomerization to the yellow forms upon visible light irradiation. The absolute fluorescence quantum yields (Φfluo.) for 1-O, 1-Y, 2-O and 2-Y (in benzene, at 298 K) are estimated to be 0.01, 0.75, 0.01 and 0.71, respectively, by Quantaurus-QY (Hamamatsu Photonics K. K.). The quantum yields of 1-Y and 2-Y are slightly smaller than those of a 4-amino1,8-naphthalimide derivative (1f in Scheme S1, Φfluo. = 0.85) used as a reference compound and previously reported ones.44–47 These decrements of the Φfluo. would be due to the small amount of the thermally generated orange forms during the measurements and the increase in the non-radiative relaxation process by the introduction to the BN-ImD unit. The fluorescence lifetime measurements for 1-O and 2-O were also performed by Quantaurus-τ (Hamamatsu Photonics K. K.). The decay curves of the fluorescence of 1-O and 2-O include three time-constant components (Figure S42 and Table S1). The shortest lifetimes of tens of picoseconds are the main decay components in the initial orange states. These results are consistent with the low fluorescence quantum yields of the orange forms, indicating that the fluorescence from the naphthalimide units is largely quenched by the electron or energy transfer from the S1 state of the naphthalimide unit to the ground state of the colored form of the BN-ImD unit. Indeed, the short lifetime components of tens of picoseconds could not be observed after the photoisomerization from the orange from to the yellow form. The energy gap (ΔG0) for the charge separation reaction between the BNImD and the naphthalimide units estimated by the Rehm-Weller equation suggests that the photoinduced electron transfer from the naphthalimide unit to the orange form of BN-ImD is energetically favorable (ΔG0 = −70 kJ/mol, supporting information). When the energy transfer from the naphthalimide unit to the BN-ImD unit proceeds in 1-O and 2-O, the C–N bond breaking reaction will be induced by the same manner with the photochromic imidazole dimer.49–51 The above mentioned conversion efficiencies of 1-O and 2-O (0.07 and 0.19, respectively) indicate that the direct linking of the naphthalimide unit to BN-ImD increases the efficiency of the conversion to the yellow form. This result implies a photoinduced electron transfer process might be involved in the photochromic reaction of 2-O. Although the fluorescence quenching behavior was also observed in the condensed mixture solution of BN-ImD and 1f, the short lifetime components of the mixture in nanosecond timescales is much longer than those of 1-O and 2-O in picosecond timescales, indicating the low efficiency of the fluorescence quenching in the mixture (Figure S44 and Table S2). The overlap integral and the Förster radius (R0) were estimated to be 5.12×1014 M−1 cm−1 nm4 and 41 Å for 1-O, and 5.06×1015 M−1 cm−1 nm4 and 60 Å for 2-O, respectively, from the eq. 1. 6

;/=

R " = 0.2108)𝜅 + Φ- 𝑛/0 ∫" 𝐼- (λ) 𝜀8 (λ)λ0 𝑑λ:

(1)

where κ2 is the orientation factor (random orientation = 2/3), ΦD is the fluorescence quantum yield of the naphthalimide unit (= 0.85), n is the refractive index (benzene = 1.501), ID (λ) is the normalized fluorescence spectrum of 1-Y or 2-Y, and εA (λ) is the molar absorption coefficient of 1-O or 2-O. Therefore, the covalent linking of BN-ImD and the naphthalimide unit is highly efficient for the fluorescence switching.

Figure 4 (a) Thermal recovery processes of the fluorescence intensity of 1 and 2 (2.9×10−6 M) at 298 K after visible light (400–700 nm, 260 mW) irradiation and (b) the pictures of the turn-on mode fluorescence switches (1 and 2, 6×10−5 M) upon 525 nm light (83 mW) irradiation under 405 nm light (10 mW).

The spontaneous thermal recovery process of the fluorescence intensity was monitored under weak 405-nm light as a fluorescence excitation light at 298 K (Figure 4 and Movie S1). The LED light at 525 nm was used as an excitation light for the negative photochromic reactions. Before 525-nm light irradiation, the solution of 1-O was dark, and any fluorescence was not observed. On the other hand, 2-O shows slight activation of the fluorescence even under 405-nm light (Movie S1), suggesting that the excitation to the naphthalimide unit of 2-O also induces the negative photochromic reaction by the energy transfer because of the direct coupling between the BN-ImD and the naphthalimide units. This becomes an advantage for a fluorescence probe under a microscopy because 405nm light takes both roles as fluorescence excitation and photochromic switching light. The bright green fluorescence drastically appeared upon irradiation with 525-nm light. These changes in the fluorescence intensity are attributed to the formations of 1-Y and 2-Y by the negative photochromic reactions. The fluorescence intensity of 1-Y and 2-Y gradually decreased over time and almost disappeared at 298 K. The rates of the fluorescence decays are almost consistent with those of the thermal back reactions of 1-Y and 2-Y at 298 K (Figure 4). The negative photochromic reactions of 1 and 2 were also observed in several kinds of polar and apolar solvents (Figure S49) although polar environment is indispensable for the classical negative photochromic molecules such as spiropyrans.21,26,32–40 In addition, the turn-on mode fluorescence switch based on the negative photochromism can be reversibly induced by irradiation with single-wavelength visible light.20 In conclusion, we developed the turn-on mode fluorescence switchable molecules by using the negative photochromism of BNImD. The absorption band at 500 nm of the stable orange form is suitable to quench the fluorescence of 4-(N,N’-dimethylamino)1,8-naphthalimide by FRET. Upon visible light irradiation, the initial orange form isomerizes to the transient yellow form, accompanied with the disappearance of the absorption band at 500 nm. This negative photochromism leads to the drastic activation of the fluorescence from the naphthalimide unit. This result indicates that fluorophores emitting at 500 nm, such as fluorescein, rhodamine, Alexa Fluor and BODIPY derivatives, will be acceptable for this negative photochromic switch. Because the fluorescent state thermally returns to the initial dark state, only single-wavelength irradiation is required to switch the fluorescence intensity. This feature will be an advantage of the thermally reversible photochromic molecule for the application to super-resolution fluorescence imaging such as PALM and STORM.

ASSOCIATED CONTENT Supporting Information Synthesis, NMR spectra, ESI-TOF-MS spectra, HPLC charts, and the other experimental results (PDF) and Movie S1 (AVI). This material is available free of charge via the Internet at http://pubs.acs.org.



AUTHOR INFORMATION Corresponding Author [email protected]

Author Contributions The manuscript was written through contributions of all authors.

Notes

The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was supported partly by the JSPS KAKENHI Grant Numbers JP18H05263, JP26107010 in Scientific Research on Innovative Areas “Photosynergetics”, and JSPS KAKENHI Grant Number JP17K14475 for K.M.

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Turn-On Mode Fluorescence Switch by Using Negative Photochromic

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