Fluorescent photochromic donor-acceptor Stenhouse adduct controlled by visible light

Article abstract of DOI:10.1016/j.dyepig.2017.09.040

A novel photochromic fluorescent DASA (donor-acceptor Stenhouse adduct) switch controlled by visible light was successfully designed and synthesized. Using 1,8-naphthalimide fluorophore in combination with indoline-based “donor” and barbituric acid “acceptor”, the DASA molecule exhibits two independent absorption bands at 440 nm and 616 nm. The physical and thermodynamic properties of fluorescent donor-acceptor Stenhouse adduct (DASA-NDI) have been investigated in different solvents. In accordance with the unique fluorescent properties under visible light/heat and H⁺/Cu²⁺, using fluorescence intensity at 604 nm (I₆₀₄) as an output and visible light, H⁺ and Cu²⁺ as inputs, a combinatorial logic gate consisting of NOR and AND logics can be described and operated.

Full text of DOI:10.1016/j.dyepig.2017.09.040

Accepted Manuscript
Fluorescent photochromic donor-acceptor Stenhouse adduct controlled by visible light
Shun Yang, Jing Liu, Zhanqi Cao, Mingming Li, Qianfu Luo, Dahui Qu
PII:
S0143-7208(17)31831-4
10.1016/j.dyepig.2017.09.040
DYPI 6265
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 29 August 2017
Revised Date: 15 September 2017
Accepted Date: 15 September 2017
Please cite this article as: Yang S, Liu J, Cao Z, Li M, Luo Q, Qu D, Fluorescent photochromic donor-
acceptor Stenhouse adduct controlled by visible light, Dyes and Pigments (2017), doi: 10.1016/
j.dyepig.2017.09.040.
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Graphical Abstract
Fluorescent Photochromic Donor-Acceptor Stenhouse Adducts Controlled by Visible
Light
by Shun Yang, Jing Liu, Zhanqi Cao, MingMing Li, Qianfu Luo*, Dahui Qu*

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Fluorescent Photochromic Donor-Acceptor Stenhouse Adduct
Controlled by Visible Light
a
a
ab
a
a
a
Shun Yang , Jing Liu , Zhanqi Cao , Mingming Li , Qianfu Luo* , Dahui Qu* ,
a Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and
Technology, 130 Meilong Road, Shanghai, 200237, China.
b College of Sciences, Henan Agricultural University, Zhengzhou 450002, China
Abstract: A novel photochromic fluorescent DASA (donor-acceptor Stenhouse adduct) switch
controlled by visible light was successfully designed and synthesized. Using 1,8-naphthalimide
fluorophore in combination with indoline-based “donor” and barbituric acid “acceptor”, the DASA
molecule exhibits two independent absorption bands at 440 nm and 616 nm. The physical and
thermodynamic properties of fluorescent donor-acceptor Stenhouse adduct (DASA-NDI) have
been investigated in different solvents. In accordance with the unique fluorescent properties under
+
2+
visible light/heat and H /Cu , using fluorescence intensity at 604 nm (I604) as an output and
+
2+
visible light, H and Cu as inputs , a combinatorial logic gate consisting of NOR and AND
logics can be described and operated.
Key words: Fluorescence; Photochromism; DASA; Logic gate
Introduction
Fluorescence, which is one of the most convenient and sensitive tools for
investigating molecular features, has various practical applications, such as
microanalysis [1] and bioimaging [2]. Typically, to avoid interference from other
fluorophores in complex system, light-controlled molecular switches can be
introduced, through which their applications including monitoring dynamic processes
in real time, can be extend [3] and optical information can be stored in memory media
[
4]. Over the past few decades, chemists have synthesized various photochromic
groups, such as spiropyran [5], diarylethene [6], azobenzene [7] and others [8-10].
However, most photochromic molecules either exhibit no fluorescence or show very

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weak fluorescence, so introducing a fluorescent unit into the photochromic molecule
is a common approach to change the fluorescent property. Upon irradiation with UV
or visible light, the enhancement or extinction of fluorescence is achieved by
energy-transfer or electro-transfer processes between fluorophores and photochromic
groups, which have been proved to be versatile as fluorescent information storage [11],
logic gates [12], cell imaging [13], and electro-optic devices [14].
The second generation aniline-based donor-acceptor Stenhouse adducts (DASAs)
have recently been reported by Read de Alaniz and co-workers as a new class of
visible light controlled molecular switches [15]. In contrast to the previously
mentioned photoswitches which generally require UV irradiation to induce their
photoisomerization, the photochromic progress of DASAs is caused by visible light,
which is favorable for the application in biological systems [16-19]. Besides, this new
photochromic switch provides a wide photoreponsive region from 500 nm to 650 nm
that is not limited to solution-state or nonpolar matrices for reversible switching
properties [20]. Moreover, the closed form of DASAs contains a cyclopentenone
group which results in the occurrence of steric hindrance, affecting the formation of
coordination compounds between copper ions (II) and the central nitrogen atoms [21,
2
2]. Significantly, upon addition of acid, the photochromic property of DASAs are
different compared with the two former isomers [23]. Consequently, the significant
changes in molecular structure and physicochemical properties associated with this
isomerization process make DASAs become attractive candidates for the use as
orthogonal photoswitch [24], actuators for drug delivery [19, 25], colorimetric

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detection [23, 26] and spatiotemporal photopatterning [27, 28]. However, to the best
of our knowledge, the combination of DASAs and fluorophores triggered by visible
light has not been previously reported.
Figure 1. (a) The schematic representation of the two isomers 6, 7 of the DASA-NDI under visible light and
darkness or heat. (b) In situ kinetic plot of the switching cycle of DASA-NDI in CHCl , monitored at λmax = 604
3
nm and 35 ºC; (c) Multiple photoswitching cycles of DASA-NDI showing 5% decrease in absorption after 10
cycles.
Herein we reported a second generation DASA and a 1,8-naphthalimide fluorophore
are combined by Suzuki-Miyaura coupling, as shown in Figure 1. Upon irradiation
with visible light, the thermodynamically unstable green “open” isomer 6 can be
converted into the photostationary yellow “closed” isomer 7 with the fluorescence
intensity of DASA-NDI increasing significantly. Moreover, the photochromic and
fluorescent properties of DASA-NDI in different solvents were investigated and
unique fluorescent properties under irradiation with certain wavelengths of visible
+
2+
light/heat and addition of H /Cu were discussed. Finally, based on its significant
advantages, DASA-NDI can be applied as a reversible fluorescent photoswitch and a

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2
+
+
combinatorial (NOR and AND) logic gate, where the Cu , H and visible light act as
input, and the fluorescence intensity acts as output.
2
Experimental section
2
.1 Materials and instrumentation
All chemicals were used as received from Adamas-beta, Acros, Aldrich, or Merck. All
solvents were reagent grade, which were dried and distilled prior to use according to
standard procedures. The molecular structures of the unknown compounds were
1
13
1
confirmed via H NMR, C NMR and High Resolution ESI mass spectroscopy. H
1
3
NMR spectra and C NMR were recorded on a Brücker AM400 spectrometer. The
HR-ESI) mass spectra were tested on a LCT Premier XE mass spectrometer. The
UV-Vis absorption spectra were obtained on Agilent Technologies Cary 60 UV-Vis
1-cm quartz cell was used). The broadband visible light irradiations were performed
(
(
by a handheld white LED lamp (YG-3896) with an output power of 1.5 W. The
fluorescence spectra were recorded on a Varian Cray Eclipse fluorescence
spectrophotometer.

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Scheme 1. Synthetic routes of DASA-NDI
2
.2 Synthesis of 4-bromo-N-butyl-1,8-naphthalimide 2
The mixture of 4-bromo-1,8-naphthalic anhydride 1 (4.00 g, 14.44 mmol) and
n-butylamine (10.60 g, 0.14 mol) in ethanol (40 mL) was refluxed under argon for 8 h.
After being cooled, the mixture was poured into water, and the precipitate was
1
collected by filtration and then recrystallized from acetic acid (4.40 g, 91.7%). H
NMR (CDCl , 400 MHz, 298K), δ (ppm): 8.66 (d, J = 8.0 Hz, 1H), 8.57 (d, J = 8.0
3
Hz, 1H), 8.42 (d, J = 8.0 Hz), 8.04 (d, J = 8.0 Hz, 1H), 7.85 (t, J= 8.0 Hz, 1H), 4.18 (t,
J= 7.6 Hz, 2H), 1.68-1.75 (m, 2H), 1.40-1.50 (m, 2H), 0.98 (t, J= 7.6 Hz, 3H).
2
.3 Synthesis of N-butyl-1,8-naphthalimide borate 3
The solution of 4-bromo-N-butyl-1,8-naphthalimide 2 (500 mg, 1.51 mmol) and
bis(pinacolato)diboron (1.10 g, 4.33 mmol) in dry dioxane (40 mL) was mixed with
potassium acetate (443 mg, 4.52 mmol), [1,1'-bis(diphenylphosphino)f

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errocene]dichloropalladium (50 mg, 0.07 mmol), and the mixture was heated to 85 ºC
under argon atmosphere. After 12 h reaction, it was cooled down and poured into
water (100 mL), then extracted with dichloromethane (50 mL × 3), and the organic
layer was separated and concentrated in vacuum. The residue was purified by column
chromatography on silica gel (petroleum ether: dichloromethane = 1:1) to afford
1
white powder (500 mg, 87.6%). H NMR (CDCl , 400 MHz, 298K), δ (ppm): 9.10 (d,
3
J = 7.6 Hz, 1H), 8.60 (d, J = 7.6 Hz, 1H), 8.56 (d, J = 7.6 Hz, 1H), 8.29 (d, J = 7.6 Hz,
1
H), 7.78 (t, J = 7.6 Hz, 1H), 4.19 (t, J = 7.6 Hz, 2H), 1.69-1.77 (m, 2H), 1.41-1.50
(m, 2H), 1.45 (s, 12H), 0.98 (t, J = 7.6 Hz, 3H).
2
.4 Synthesis of 5- (N-butyl-1,8-naphthalimide)-indoline 4
A stirred solution of N-butyl-1,8-naphthalimide borate 3 (100mg, 0.27 mmol) and
-bromoindoline (45.22 mg, 0.23 mmol) in dioxane (15 mL) 5-bromoindoline
charged with K CO aqueous solution (5 mL),
tetrakis(triphenylphosphine)palladium (Pd(PPh ) ) (21 mg, 0.02 mmol), and the
5
2
M
2
3
3
4
mixture was heated to 100 ºC under argon atmosphere. After 2 h stirring at this
temperature, it was cooled and poured into water (15 mL), then extracted with
dichloromethane (15 mL × 3), the organic layer was separated, and washed with
saturated brine solution and dried over MgSO , then concentrated in vacuum. The
4
residue was purified by column chromatography on silica gel (petroleum ether: ethyl
1
acetic =10:1) to obtain pale yellow solid in 56% yield (57 mg). H NMR (CDCl , 400
3
MHz, 298K), δ (ppm): 8.61(m, 2H), 8.41 (dd, J = 4.4, 0.8 Hz, 1H), 7.67 (m, 2H), 7.27

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(d, J = 8.0 Hz, 1H), 7.17 (dd, J = 8.0, 4.0 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 4.20 (t, J
=
7.6 Hz, 2H), 3.69 (t, J = 4.4 Hz, 2H), 3.15 (t, J = 8.2 Hz, 2H), 1.73 (m, 2H), 1.45
13
(
m, 2H), 1.0 (t, J = 8.0 Hz). C NMR (CDCl , 100 MHz), δ (ppm): 163.5, 163.3,
3
1
1
51.1, 146.8, 132.1, 130.0, 129.9, 129.2, 128.8, 128.6, 128.0, 127.9, 126.5, 125.3,
21.8, 119.7, 112.4, 108.8, 108.0, 59.4, 46.5, 39.2, 29.2, 28.6, 26.8, 19.4, 12.8. HRMS
+
(
ESI) (m/z): [M+H] calcd for C H N O , 371.1754; found, 371.1751.
2
4
23
2
2
2
.5
Synthesis
of
5
-((2Z,4E)-5-(5-(2-butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)indolin
-1-yl)-2-hydroxypenta-2,4-dien-1-ylidene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-t
rione 6
A mixture of 5- (N-butyl-1,8-naphthalimide)-indoline 4 (40 mg, 0.11 mmol) and
barbaturic acid furan adduct 5 (23.4 mg, 0.1 mmol) was stirred at room temperature in
DCM (1 mL) until the reaction was completed (monitored by TLC). The crude
mixture was added with DCM (1 mL) and sonicated for 1 min. The mixture was then
added to vigorously stirring hexane (50 mL) dropwise. The product was filtered and
washed with hexane to afford blue crystals in 72% yields (44 mg). The equilibrium
state of DASA-NDI includes 22% isomer 6 and 78% isomer 7 (Fig. S6-S7). NMR
1
characterization is cyclized DASA-NDI 7. H NMR (CDCl , 400 MHz, 298K), δ
3
(ppm): 8.61 (m, 2H, naphthalene-H), 8.37 (dd, J = 8.0, 4.0 Hz, 1H, naphthalene-H),
7
.73 (m, 1H, naphthalene-H), 7.69 (m, 1H, naphthalene-H), 7.64(m, 1H, indoline-H),
7
.18(m, 1H, indoline-H), 6.61 (m, 1H, indoline-H), 6.48 (dd, J = J = 8.0 Hz, 1H,
1
2

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cyclopentenone-H), 5.50 (m, 1H, cyclopentenone-H), 4.22 (t, J = 8.0 Hz, 2H,
naphthalene-H), 4.05 (m, 1H, barbaturic acid-H), 3.83 (m, 1H, cyclopentenone-H),
3
.66 (m, 2H, indoline-H), 3.44 (m, 1H, cyclopentenone-H), 3.38 (s, 3H, barbaturic
acid-H), 3.19 (s, 3H, barbaturic acid-H), 3.16 (m, 2H, indoline-H), 1.73 (m, 2H,
naphthalene-H ), 1.47 (m, 2H, naphthalene-H), 0.98 (t, J = 8.0 Hz, 3H,
1
3
naphthalene-H). C NMR (CDCl , 100 MHz), δ (ppm): 202.9, 167.2, 166.8, 164.4,
3
1
1
3
6
64.2, 162.5, 151.1, 150.9, 147.2, 134.8, 132.8, 131.1, 131.0, 130.6, 130.1, 129.6,
28.9, 127.5, 127.0, 126.5, 126.5, 123.0, 121.0, 106.0, 60.1, 48.1, 47.6, 46.8, 40.2,
+
0.2, 29.0, 28.7, 28.1, 20.4, 13.9. HRMS (ESI) (m/z): [M-H] calcd for C H N O ,
39
31
4
6
03.2249; found, 603.2239. (For details, see Support Information, Fig. S4-S8).
3
3
3
Results and discussion
.1 Spectral properties
.2.1 Photochromic properties of DASA-NDI
The photochromic characteristics of DASA-NDI have been measured in three
different solvents at 293 K with alternating irradiation by broadband visible light and
heat in 310 K, and itsrepresentative absorption spectra and fluorescence spectra are
shown in Table 1. The absorption bands for indoline-DASA was approximately at 616
nm and 438 nm in different solvents, which was consistent with the absorption of
native indoline-DASA (λmax = 615 nm) in previous report [15]. Besides, compared
with the absorption band of 4 (λmax = 360 nm), the reason for bathochromic shift in
absorption band of DASA-NDI (λmax = 438 nm) might be homoconjugation that

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enhanced hybridization of molecular orbitals between the electron-rich donors and
acceptor groups (Fig. 2, Fig. S9).
The molar absorptivities (ε) for DASA-NDI in toluene, trichloromethane and
acetonitrile were determined through a combination of NMR and absorption
6
-1
-1
spectroscopies at equilibrium state, uniformly high at ~10 M cm , which agrees
with the previous investigation and proves that the change of colour between dilute
solutions of the two states could be visually monitored easily [15] (Fig. S10, Table
1
S1). Moreover, as is shown in H NMR spectroscopy, the percentage of open form of
DASA-NDI in CDCl was ca. 22 % at equilibrium state, which was essential in
3
observing the photochromic properties. Additionally, the key signals at δ = 12.44,
8
.26, 7.47, 7.41 ppm were attributed to the protons on triene of open isomer 6 (Ha-d).
Upon visible light irradiation, these signals were disappeared and the chemical shifts
at δ = 6.48, 5.50, 4.05, 3.83, 3.44 ppm were attributed to the protons on
cyclopentenone or barbaturic acid (Ha’-d’). (Fig. S7)
Upon continued irradiation with visible light, the green solution of DASA-NDI in
CHCl was converted into pale yellow, and the absorption band of it decreased at 623
3
nm but increased at 442 nm with the blue shift of the absorption band, which is due to
the reversible thermal 4π electrocyclic reaction. After being placed at 35ºC for 20 min,
the color of solution returned green and the absorption spectra nearly recovered to its
1
initial state (Fig.2a and 2c). Moreover, H NMR spectroscopy and absorption
spectroscopy indicting that the opening and closing rates and activation energies (EA)
of DASA-NDI were comparable to experimental results obtained by Alaniz (Table 1)

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[
15].
Figure 2. Absorption spectral changes (a, b) and fluorescence spectral changes (c, d) of DASA-NDI upon
2
-4
irradiation with broadband visible light (1.5 mW/ cm ) in CHCl (5.5 × 10 M) and upon heating at 35ºC after
3
irradiation. The irradiation time for each step was 15 s. The heat time for each step was 5 min.
Entr
y
Photochromism
Fluorescence
Solve λ nm (ε, E
Eclosed
Cycl λex (nm) λem
φ
φ
A
open
ex
ope
ex
clos
-1
nt
L
mol (kJ/mol) (kJ/mo izati
(n
-1
n
ed
cm )
l)
on
m)
rate
-
1
(
s )
*
100
5
1
Tolue 438 (3.4·10 )
60
65
2.84
438
534 0.2 0.5
ne
1
6
5
6
16 (3.0·10 )

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6
2
Trichl 442 (1.2·10 )
58
57
63
63
61
68
2.91
2.87
2.96
442
441
---
654 0.2 0.4
orom
ethan
e
3
6
6
6
23 (1.1·10 )
594
604
5
3
Aceto 441 (8.5·10 )
573 0.0 0.0
nitrile
2
2
5
6
19 (4.6·10 )
5
Alan CD
C 615 (1.1·10 )
---
---
2
iz
15]
l
2
[
Table 1. Spectral characteristics of initial and photoinduced forms of DASA-NDI 6, 7 in different
-5
solvents (5.5 × 10 M) at 298K.
In order to examine the reversibility and stability of DASA-NDI in
trichloromethane, an extensive cycling test was performed via Pump-probe absorption
spectroscopy with a broadband white LED for excitation and a heated stage for
equilibration (35 ºC in trichloromethane, 22% open form at equilibrium state
1
indicated by H NMR spectrum). During the first cycle, a detailed plot of absorption
at λmax (623 nm) was shown in Fig. 1b, and the following 10 cycles were measured by
following photostationary state and thermal equilibration (Fig.1c). Through fatigue
experiments, this rapid and complete switching of DASA-NDI (5% loss after 10
cycles) demonstrated the robust nature of this progress.
+
2+
3
.2.2 Fluorescent properties of DASA-NDI under visible light/heat and H /Cu
T
he significant absorbance changes in the visible region, associated with the
photoinduced transformation of a triene to cyclopentenone, can be exploited to
activate an energy-transfer pathway and control the emission of the fluorescent partner.

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As is shown in Fig. 2, upon irradiation with visible light (λ= 442 nm) in CHCl3
solution, the DASA-NDI can be activated, and two fluorescence bands appear in the
wavelength region of 520-620 nm for closed-ring isomer 7 and 620-720 nm for 6,
respectively. The initial state including 6 and 7 gave relatively weak fluorescence.
Meanwhile, the peak absorption of DASA-NDI was around 620 nm and the
significant overlap between it and the emission of the isomer 7 permits the transfer of
energy from the fluorescent to the photochromic fragment, which results in the lower
fluorescence intensity. However, upon brand visible light illumination for 105 s, the
triene switches to the corresponding cyclopentenone to form 7 with the decrease of
characteristic absorption of 6 (λ= 620 nm), the absorption at the wavelength of 442
nm enhanced, and the disappearance of corresponding emission band (λ= 620-720
nm), leading to the enhancement of fluorescence intensity. All these changes are due
to the lack of any overlap between the emission of the fluorophore and the absorption
of the photochrome that prevents the transfer of energy.

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Figure 3. The absorption spectral and fluorescence spectral changes of DASA-NDI in CHCl
3
+
2+
solution (20 µM) upon addition of various amounts of H (a, b) and Cu (c, d). Moreover,
corresponding photographs before and after illumination with visible light also shown on the top
2
+
of spectra. Cu is derived from cupric acetate (Cu (OAc) ) and dissolved in the mixed solvent of
2
4
+
CHCl /MeOH (3:2) and H is derived from CF COOH and dissolved in CHCl .
3
3
3
Besides, the fluorescence quantum yields of the DASA-NDI (φopen and φclosed) in
various solvents, using Rhodamine B (RhB) in 0.1 M EtOH as a reference, showing
that both the emission intensity and quantum yields were sensitive to visible light,
namely, the parameters increase under visible light irradiation (Table 1, Fig. S11) [29].
Moreover, after 105 s illumination, the photostationary state 7 has a lifetime of 25 min
under heating in 35ºC and eventually reverts back to the mixture of original isomer 6
and 7. As a result, the initial absorption and emission spectra were almost fully
restored in a few minutes under heat.

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+
Furthermore, upon addition of various amounts of H in CHCl solution of
3
DASA-NDI, the intensity of the absorption band at 430 nm and 623 nm decreased
and the fluorescence intensity at 589 nm and 660 nm declined continuously. The two
+
solutions of DASA-NDI before and after adding 30 µM H showed green color, but
upon irradiation of two green solutions with visible light, the solution without acid
addition became yellow and its fluorescence intensity was significantly enhanced, yet
the other with the addition acid did not change at all. The reason for this difference is
that the acid protonates the tertiary amine on the indoline which results in the
prohibition of the photo-induced isomerization of DASA-NDI (Fig. 3a-3b). Besides,
2
+
upon adding different amounts of Cu in CHCl solution of DASA-NDI, the intensity
3
of the absorption bands at 430 nm and 623 were decreased a bit and the absorption
band at 430 nm shifted to blue obviously and the fluorescence intensity at 589 nm and
6
60 nm declined sharply, which is due to the weak coordination effect of cooper ions
and tertiary amines on the indoline. Significantly, as shown in Fig.3c and 3d, after
2
+
irradiation of DASA-NDI and DASA-NDI-Cu with visible light, the former became
yellow and the later became yellow-green due to the influence of ions, but the
2
+
fluorescence intensity of DASA-NDI-Cu increased remarkably, which is probable
due to the photoisomerization that destructs the weak coordination between cooper
ions and nitrogen atoms.

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Figure 4. The DASA-NDI-based combinatorial (NOR and AND) logic gate; (a) The fluorescence spectra of
DASA-NDI under different inputs and (b) their corresponding value of FL intensity at 604 nm. (c) Design strategy
and logical expression. Only in the presence of visible light input (0/0/1), the FL intensity increased (output = 1),
otherwise output was “0”. (d) A truth stable of the combinatorial logic gate.
3
.2.3 Fluorescent photochromic switch and logic gate
As a basic binary unit, the fluorescent chemosensor combined with a molecular
switch offers a possibility for establishing electronic logic devices. Based on the new
fluorescent photochromic switch (DASA-NDI), a combinatorial (NOR and AND)
logic gate system can be designed (Fig. 4c). With respect to inputs, the presence and
2
+
absence of broadband visible light irradiation as well as the addition of Cu and the
+
control of H was defined as “1” and “0”, respectively. The fluorescence of
+
2+
DASA-NDI, acting as outputs, can be controlled by using visible light, H or Cu to
switch between the open (low-fluorescent, I ≤ 1000) and closed (high-fluorescent, I ≥
1
000) state, where I is the value of fluorescence intensity at 604 nm. If the value of I

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locates under 1000, the corresponding output is considered as the “1” state, otherwise,
it is considered as the “0” state (Fig. 4a and Fig. 4b).
Therefore, according to the truth table shown in Fig. 4d, a combinatorial logic gate
integrated within a single molecule was approached. Only the presence of visible light
input (0/0/1) could enhance the fluorescence intensity of DASA-NDI (output = 1)
indicated complete photoisomerization of DASA-NDI; while those in the absence and
presence of three inputs (0/0/0, 1/1/1) or in the presence of either input expect visible
light or both inputs (1/0/0, 0/1/0, 0/1/1, 1/0/1, 1/1/0) remain low-fluorescent or nearly
non-fluorescent, which can be confirmed by testing the fluorescence intensity
responses (Fig. 4a-4b).
Conclusion
In conclusion, a novel fluorescent photochromic DASA-NDI whose fluorescence
could be flexibly controlled by visible-light/heat and ions/protons were successfully
designed and conveniently synthesized by Suzuki-Miyaura coupling of combining a
fluorescent unit, 1,8-naphthalimide and a second generation DASA photoswitch. The
photochromic and fluorescent properties of DASA-NDI have been investigated under
certain visible light in different solvents, which results in the application of a
reversible fluorescent photoswitch and a combinatorial (NOR and AND) logic gate.
We envision that this novel visible light strategy will afford an efficient and green
method for construction of photochromic fluorescent switching and advance the study
of various photoswitches.

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Acknowledgement
We thank the support of NSFC/China (21672060), the Fundamental Research
Funds for the Central Universities (WJ1616011, WJ1213007, 222201717003), the
Programme of Introducing Talents of Discipline to Universities (B16017).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
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Highlights
A novel photochromic donor-acceptor Stenhouse adduct was successfully constructed for fluorescent
photoswitch.
.
The photochromic fluorescent switch could be flexibly tuned not only by visible-light/heat but also by
ions/protons.
A combinatorial logic gate consisting of NOR and AND logics was further constructed based on the
favorable optical and chemical properties of the adduct.