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Physical Chemistry Chemical Physics Accepted Manuscript

Cite this: DOI: 10.1039/c0xx00000x

www.rsc.org/pccp PAPER
Experimental and theoretical study of enol-keto prototropic
tautomerism and photophysics of azomethine-BODIPY dyads†
Zhong-Hua Pan,a Jing-Wei Zhoub and Geng-Geng Luo,*a
Received (in XXX, XXX) Xth XXXXXXXXX 2014, Accepted Xth XXXXXXXXX 2014
5 First published on the web Xth XXXXXXXXX 2014
DOI: 10.1039/b000000x

In this study we report about two novel azomethine-BODIPY dyads 1 and 2. The two dyads have been respectively
synthesized by covalent tethering of tautomeric ortho-hydroxy aromatic azomethine moieties including N-salicylideneaniline
(SA) and N-naphthlideneaniline (NA) to a BODIPY fluorophore. Both of the two dyads 1 and 2 show enol-imine (OH) structures
10 dominating in the crystalline state. Dyad 1 in the enol state is the most stable form at room temperature in most medium, while
enol-keto prototropic tautomerism of NA moiety in solution is preserved in the dyad 2, which can be reversibly converted
between enol and keto forms in the environment’s polarity. Visible illumination of the dyad 2 in the enol state excites
selectively the BODIPY fragment and then deactivates radiatively by emitting green light in the form of fluorescence, while the
emission intensity of 2 in the keto state is quenched on the basis of proton-coupled photoinduced electron transfer (PCPET)
15 mechanism. This allows large fluorescence modulation between the two states of the dyad 2 and generates a novel
tautomerismable fluorescent switch. Theroretical calculations including calculated energies, potential energy surface (PES) and
intrinsic reaction coordinate (IRC) analysis further support single proton transfer reaction from enol form to transition state (TS)
and from the TS to keto form for 2 is easier to occur than that of 1, which accounts for the fluorescence quenching of 2 in
methanol. The agreement of the experimental results and theoretic calculations clearly suggests that fluorescent and tautomeric
20 components can be paired within the same molecular skeleton and the proton tautomerization of the latter can be designed to
regulate the emission of the former. In addition, preliminary experiments revealed that 1 can be potentially used as a simple
on/off fluorescent chemosensor which exhibited higher selectivity for Cu 2+ over other common cations.

proton transfer in these systems causes a change in optical

1. Introduction properties, these molecules can be utilized for the design of
40 various optical switches and storage devices.5 According to
Tautomers are readily interconverted constitutional isomers,
significances of proton transfer and tautomerism processes,
25 usually distinguished by a rearrangement of a labile hydrogen
there have been the subject of numerous studies of the ortho-
atom and a double bond (e.g., enol-keto tautomerization).1 The
hydroxy aromatic azomethines in the solid-state and in solution.
equilibrium between tautomers is often rapid under normal
Generally, they display two possible tautomeric forms, the enol-
conditions, being catalyzed by traces of acid or base present in
45 imine (OH) form and the keto-enamine (NH) form. Depending
most samples and solvents.2 Proton tautomerization is central to
on the tautomers, two types of intramolecular hydrogen bonds
30 several fields of chemistry and biochemistry and plays a role in
are observed in the ortho-hydroxy aromatic Schiff bases: O-
pharmaceutical action, enzyme activity, stabilization of base
H···N in enol-imine and N-H···O in keto-enamine tautomers.
pairs in duplex DNA, and self-assembly.3,4 Ortho-hydroxy
The enol-imine form is the most stable form at room
aromatic azomethines (known as Schiff bases) possessing
50 temperature but is in equilibrium with the keto-enamine form
intramolecular hydrogen-bonding are an interesting class of
relying on the substitution patterns of the aromatic rings and the
35 compounds for theoretical and experimental studies because
surrounding medium.6 Different analytical methods have been
they can undergo proton-tautomerism reaction leading to
used to show the presence of the enol-imine and keto-enamine
interesting properties including thermo- and phtochromism. As
forms, among them are UV-vis, fluorescence, Raman, FT-IR,
a
College of Materials Science and Engineering, Huaqiao University, 55 NMR spectroscopy and X-ray crystallography techniques, as
Xiamen 361021, P. R. China; E-mail: [email protected]; Fax: 86-592- well as combinations thereof.7 As a complement to these
6162225. experiments, a variety of computational chemistry methods also
b
School of Pharmaceutical Sciences, East Campus, Sun Yat-sen
University, Guangzhou 510006, P. R. China has been applied.8 Both experimental and theoretical
† Electronic Supplementary Information (ESI) available. Additional investigations have shown that the reversible enol-keto
calculations and experimental measurements, figures and tables. CCDC 60 tautomerism occurs via an intramolecular H-transfer mechanism
reference numbers 1000809-1000810. For ESI and crystallographic data
between the ortho-hydroxy and the imine nitrogen.8 Enol-keto
in CIF or other electronic format see DOI:10.1039/b000000x.

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tautomerism has been used to modulate magnetic dynamics of on the photophysics of BODIPY chromophores, azomethine-
some lanthanide complexes.9 However, relatively less attention BODIPY dyads 1 and 2 functionalized with imines were
has been paid to attachment of ortho-hydroxy azomethine prepared by convenient one-step condensation reaction of 3
fragments into organic chromophores to study the effect of 45 with 2-hydroxybenzaldehyde or 2-hydroxynaphthaldehyde in a
5 enol↔keto tautomerism reaction on photophysical properties of high yield according to the synthetic procedures along with
chromophores. individual Schiff bases (SA and NA) as well as a model TM-
Seeking to look for suitable organic chromorphores in favor BODIPY, as shown in Scheme 1. Dyads 1 and 2 were first
of grafting tautomeric components, our attention has turned to documented from single-crystal X-ray crystallography
the boron dipyrromethene (4,4-difluoro-4-bora-3a,4a-diaza-s- 50 (SCXRD) and further characterized by standard analytical
10 indacene, BDP or BODIPY) class of dyes. Recent efforts in techniques (i.e., FT-IR spectra, NMR spectroscopy, mass
other groups and our laboratory have focused on developing spectrometry, elemental analysis and cyclic voltammetry),
BODIPY fluorescence sensors based on photoinduced electron which gave satisfactory data corresponding to their molecular
transfer (PET) as a transduction mechanism.10 BODIPYs are structures. Solid-state IR spectra of 1 and 2 were recorded in the
well-known for their excellent photophysics such as strong 55 4000-400 cm-1 region (Fig. S1 of ESI†). Generally, the non-
15 absorption of visible light, high fluorescence quantum yields hydrogen-bonded or a free hydroxyl group absorbs strongly in
and good photostability.10,11 In addition, the optical properties the 3550-3700 cm-1 region.13 Intramolecular hydrogen bonding
of BODIPY are tunable through structural modifications on the if present in the six-membered ring system would reduce the O-
core of dye. These favorable features render BODIPY as widely H stretching band to 3550-3200 cm-1 region.14 IR spectra of 1
used as a fluorophore core for the construction of luminophores, 60 and 2 show a sharp band at 3441 and 3442 cm-1 due to O-H
20 molecular probes or molecular logic gates, light-harvesting stretching vibration. The characteristic region of 1700-1500 cm-
molecular arrays and photodynamic therapy (PDT) agents.11 In 1
can be used to identify the proton transfer of Schiff bases.
this context, we decided to explore the possibility of integrating Azomethine (C=N) bond stretching vibration was observed to
fluorescent and tautomeric components within the same be 1623 and 1626 cm-1 for 1 and 2. The crystal phase purities of
molecular skeleton. We report herein the synthesis, structures, 65 1 and 2 were confirmed from powder X-ray diffraction (PXRD)
25 photophysical properties of two dyads (1 and 2) with high patterns (Fig. S2 of ESI†). The thermal behavior of 1 and 2 as
thermal stabilities, which consist of ortho-hydroxy aromatic well as SA and NA was studied by differential scanning
azomethines including N-salicylideneaniline (SA) and N- calorimetry (DSC) (Fig. S3 of ESI†). The DSC thermogram of
naphthlideneaniline (NA) coupled to a BODIPY fluorophore. 1 and 2 exhibited only one exothermic peak at 288 ºC (∆H =
Significant differences in the photophysical behaviours of the 70 107.9 J g-1) and 299 ºC (∆H = 86.21 J g-1), respectively,
30 synthesized two dyads related with proton-tautomerism are ascribed to the melting point (Tm) of dyads. Obviously, the two
observed and discussed with the aid of density functional theory dyads exhibit the higher melting point and more stable than that
(DFT) calculations. of starting material 3 (Tm = 190 ºC) or references of Schiff
bases SA (Tm = 52±1 ºC) and NA (Tm = 96±1 ºC).
75 The redox behaviour of the two dyads were investigated
using the cyclic voltammetry (CV) technique in dry DCM
containing 0.1 M TBAP background electrolyte (Table S1 of
ESI†). For these dyads, a single electrochemically peak is
observed on reductive scans that could be ascribed to formation
80 of the BODIPY π-radical anion (-1.69 V for 1 and -1.59 V for
2). On oxidative scans, two peaks corresponding to the
Scheme 1 Design and synthesis of dyads 1 and 2. oxidation of Schiff base fragment, and the formation of the
BODIPY π-radical cation are observed for 1 and 2. For 2, slight
2. Result and discussion negative shift of oxidation peak from Schiff base fragment (0.62
85 V) compared with that of 1 (0.80 V) due to the redundant
35 2.1. Synthesis and characterization
benzene ring. The oxidation potentials of BODIPY moiety in
The starting BODIPY-linked aniline 3 was firstly synthesized these dyads is similar (1.01 V for 1, and 1.04 V for 2). From
in moderate yield from a reaction of 2,4-dimethylpyrrole and 4- these results of electrochemistry, it is inferred that the Sciff base
nitro-benzaldehyde, followed by a conversion of the –NO2 unit and BODIPY group are isolated and only minor, if any,
group to form an –NH2 substitute according to reported 90 electronic communication takes place through the bridge in the
40 procedures.10e,12 With the main aim of investigating the effect of groud state.
prototropic tautomerism of ortho-hydroxy aromatic Schiff bases 2.2. Crystal structural analyses

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tautomers, whereas these bonds display single bond character in
the enol-imine tautomers. The C7-N1 and C11-N1 bond are also
double bonds in the enol-imine tautomers and of single bond
length in the keto-enamine tautomers. SCXRD reveals the
50 preference of enol structure in the Schiff base moiety in the
solid state for 1 and 2, as indicated by the bond parameters (C5-
O1 = 1.359 Å, C7-O1 = 1.329 Å and C7-N1 = 1.285 Å, C11-N1
= 1.291 Å). Furthermore, the aromaticities of enol forms of 1
and 2 can be also inferred from the harmonic oscillator model
55 aromaticity (HOMA) index.16 The HOMA indices in the range
Fig 1 Single crystal X-ray diffraction structures of 1 (a), 2 (b) with of 0.900-0.990 and 0.500-0.800 correspond to aromatic and the
thermal ellipsoids set at 50% probability, and the theoretical geometric non-aromatic rings, respectively. In 1, the calculated HOMA
structures of 1 (c) and 2 (d). indices for C1/C6 and C8/C13 are 0.968 and 0.992. These
Crystalline samples of azomethine-BODIPY dyads 1 and 2 results show that C1/C6 and C8/C13 in 1 have purely aromatic
5 were obtained by a slow vapour diffusion of hexane into a 60 character. In 2, the calculated HOMA indices for C5/C10 and
saturated CHCl3 solution of 1 or CH2Cl2 solution of 2. Single C12/C17 are 0.629 and 0.995, which display that C12/C17 has
crystals collected were of suitable quality to undertake a purely aromatic character while C5/C10 is deviated from
structure determination by SCXRD analysis, and aromaticity. This difference in molecular configuration is
crystallographic data are given in Table S2 (ESI†). Both 1 and 2 responsible for different results of theoretical calculations and
10 crystallize in the triclinic space group Pī with one independent 65 optical properties as discussed below.
molecule within the asymmetric unit (Fig. 1a, b). In fact, each Table 1 Experimental and theoretical hydrogen-bond geometries (Å,
azomethine-BODIPY dyad constitutes a BODIPY unit as the deg) for 1 and 2.
fluorophore and a Schiff base fragment as tautomerism. As D-H···A D-H H···A D···A D-H···A
previously observed in some similar structures,10d,15 the
X-ray diffraction for 1 1.02(4) 1.65(5) 2.605(4) 153.8(3)
15 BODIPY core B(N2F2) shows a quasi-tetrahedron configuration
B3LYP/6-31+G(d,p) for 1 1.00 1.74 2.634 147.2
with the average angle of F-B-F of 108.8º and the average bond X-ray diffraction for 2 1.02(2) 1.61(3) 2.548(2) 150.9(2)
length of B-N and B-F to be 1.544 Å and 1.388 Å, respectively B3LYP/6-31+G(d,p) for 2 1.01 1.65 2.563 148.0
(Table S3 of ESI†). On the BODIPY moiety, the C9BN2 The existence of strong intramolecular O1-H1D···N1 and
framework consisting of one central six-membered and two O1-H1B···N1 hydrogen bonds both producing S(6) ring motifs
20 adjacent five-membered rings is essentially flat, with the 70 is observed in 1 and 2, respectively. These H-bonds can be
maximum deviation from the least-squares mean plane for the characterized by O1···N1 distances and are summarized in
12 atoms of the indacene group being 0.083 Å in 1 and 0.029 Å Table 1. It is known that there is a strong correlation between
in 2, respectively. This geometry indicates the strongly the strength of the H-bond and the delocalization of the system
delocalized π-system nature of the C9BN2 framework in 1 and 2. of conjugated double bonds, and the effect is qualitatively
25 However, this π-electron delocalization is interrupted between 75 interpreted by resonance-assisted hydrogen bond (RHAB)
the two B-N bonds (1.536-1.554 Å), which is in agreement with model.17 The observed O···N distance of 2.605(4) Å for 1 and
the results reported for other BODIPYs.15 Introduction of two 2.548(2) Å for 2 are apparently shorter than 2.656 Å which was
methyl groups at C-1 and C-7 positions in the BODIPY core in reported for O-H···N in the class of RAHB model. The
1 and 2 were revealed to prevent the free rotation of the meso- aggregations of 1 and 2 through a series of weak hydrogen
30 phenyl moiety, resulting in almost orthogonal configuration 80 bonds including C-H···F and edge-face C-H···π interactions in
between the BODIPY core and meso-benzene moiety. The the crystal cells are shown in Fig. S4 of ESI†. These F- and C-
dihedral angle between the meso-phenyl ring and the indacene based interactions can be further visualized by Hirshfeld surface
plane (87.6º) in 1, is analogous to that in 2 (86.5º), indicating calculations and given in Fig. S5 of ESI†.
the almost nonelectronic coupling nature between the meso-
2.3. Computational studies
35 phenyl ring and C9BN2 unit in 1 and 2.
From the ORTEP view, the dihedral angle between the 85 The optimized parameters (bond lengths, bond angles, and
aromatic ring systems in the Schiff base moiety of 1 is 26.1º. dihedral angles) of dyads 1 and 2 have been obtained using the
This dihedral angle decreases to 4.1º in 2. In general, ortho- Gaussian 09 program with density functional theory (DFT), the
hydroxy Schiff bases undergo tautomerism involving proton B3LYP method, and 6-31+G(d,p) as the basis set. The
40 transfer from the hydroxylic oxygen to the imino nitrogen atom. optimized structures of 1 and 2 are depicted in Fig. 1c and Fig.
The process of proton transfer ends up with two tautomeric 90 1d with numbering of the atoms. The calculated structural
forms known as enol and keto structure. The C7-N1 and C5-O1 parameters of 1 and 2 are presented in Table S3 along with the
bond for 1 as well as C11-N1 and C7-O1 bond for 2 are the corresponding values obtained from the experimental data.
most important indicators of the tautomeric types. The C5-O1 When the X-ray structures of 1 and 2 are compared to their
45 and C7-O1 bond are of double bonds for the keto-enamine optimized counterparts, the bond lengths and bond angles

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computed by B3LYP method show a good correlation with the enol-imine geometry by selecting O-H bond as redundant
experimental values. The remarkable conformational internal coordinate. The graph of the relative energy versus the
discrepancies are observed in the orientation of meso-phenyl 50 O-H bond distances is given in Fig. 2. The energy values were
ring in 1 and 2. The orientation of meso-phenyl ring is defined calculated relative to the energy of the stable enol form. Fig. 2a
5 by the torsion angles C7-N1-C8-C13 [153.1(2)º for 1] and C11- shows two minima representing the stable forms of 1. The keto
N1-C12-C17 [177.2(1)º for 2]. These torsion angles have been form corresponds to a local minimum while the global
calculated at 145.06º and 146.11º for B3LYP, respectively. minimum represents the stable enol form. The potential energy
Such conformational discrepancies can be explained by the fact 55 barrier needed for the enol to keto form conversion process in 1
that the calculations assume an isolated molecule where the was calculated as 6.08 kcal mol-1.
10 intermolecular Coulombic interaction with the neighboring
molecules are absent, whereas the experimental result
corresponds to interacting molecules in the crystal lattice, as
described in the aforementioned crystal structure analysis.
When the geometries of hydrogen bond in the optimized
15 structures of 1 and 2 are examined, it is seen that O-H···N
intramolecular hydrogen bonds exist between the phenol O
atom for 1 (naphthol O atom for 2) and imine N atom. For 1, O-
H, H···N, and O-H···N values are 1.02(4) Å, 1.65(5) Å, and
153.8(3)º for X-ray diffraction, and 1.00 Å, 1.74 Å, and 147.2º
20 for B3LYP. For 2, O-H, H···N, and O-H···N values are 1.02(2)
Å, 1.61(3) Å, and 150.9(2)º for experimental data, and 1.01 Å,
1.65 Å, and 148.0º for theoretical values. There are good
matching between the calculated hydrogen-bond geometries and
those obtained from the X-ray diffraction structures. The
25 presence of the hydrogen bond appears as an important property
of the molecule, stabilizing its conformation in the crystal; as
shown in the molecular modelling part, this is also visible in the
model obtained for the molecules discussed.

Fig 2 Relative energy profiles during the proton transfer process of 1 (a)
30 and 2(b).

The enol-imine (NH) and keto-enamine (OH) tautomerisms

of dyads 1 and 2 are given in Scheme S1. To investigate these
tautomeric stabilities, quantum chemical calculations were
carried out for the enol and keto forms of 1 and 2. Some Fig 3 Transition state from enol to keto form of 1 (a) and 2(b) at the
B3LYP/6-31+G(d,p) level (kcal mol-1).
35 important physicochemical properties such as total, HOMO, and
LUMO energies and dipole moment (µ) were also calculated We have also considered 2 for further study to know whether
with the same level of theory, and the results are given in Table 60 the nature of proton transfer of 1 and 2 is the same. As seen
2. First comparing the total energies of the two tautomers for 1, from Table 2, the calculated total energy of the enol form of 2 is
the enol tautomer is substantially more stable (4.91 kcal mol-1) only slightly lower than the keto form in the gas phase (0.81
40 than the keto form. This is an expected result since the enol kcal mol-1). Similar to the dyad 1, PES scan of 2 shows two
form of 1 has two purely aromatic rings as supported by the distinct minima corresponding to enol and keto tautomers. Here
above structural analysis and ortho-hydroxy azomethine 65 the enol form is slightly stable than keto form. The energy
generally prefers the enol structure. The intramolecular proton barrier in going from enol to keto form is 3.34 kcal mol-1, which
transfer for 1 was investigated in the gas phase by performing a is obviously smaller than that of 1. Such a small energy barrier
45 potential energy surface (PES) scan process at the B3LYP/6- is easily overcome by a light-weight particle, such as a proton at
31+G(d,p) level in order to determine its effects on the room temperature. Therefore, at ground state there will be
molecular geometry. The process was started from optimized 70 always a mixture of keto and enol forms with larger percentage

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of enol form in gas phase and keto form in solution, absorption spectra of the studied dyads exhibit features that can
respectively. be easily assigned to specific subunits. SA exhibits two
To further examine the whole process of enol-keto moderate absorption peaks centered at 269 nm and 348 nm,
tautomerization via single proton transfer in the dyads 1 and respectively, assignable to π→π* and n→π* transition.18 The
5 2 in more detail, we performed an intrinsic reaction 50 model TM-BODIPY presents a sharp and intense absorption
coordinate (IRC) analysis for each case (see Supporting peak at 500 nm (Fig. S8 of ESI†),19 a typical feature for the
Information). The nature of the stationary points was BODIPY dyes.15 The absorption spectrum of the dyad 1 is
confirmed by means of a vibrational analysis. The whole nearly the superposition of the spectra of SA and TM-
prototropic tautomerism process of 1 and 2 is actually BODIPY. The absorption maximum (499 nm) of 1 with molar
10 subdivided into two parts: (i) transfer from the enol form 55 absorptoin coefficient as high as 8.03×104 M-1 cm-1 is as
(OH) to the transition state (TS), and (ii) from the TS to the expected for TM-BODIPY dye, which is due to the 0-0
proton transfer keto form (NH). Fig. 3 shows calculated free vibrational band of the S0→S1 (π-π*) transition localized on the
energy profiles and the structures of enol form, TS, and keto BODIPY unit.19
form for 1 and 2. For enol-keto tautomerization of 1, the free
15 energy of keto form is very close to that of TS (3.4 kcal mol-
1
vs 3.5 kcal mol-1) while large than which of enol form (3.4
kcal mol-1 vs 0 kcal mol-1). While for 2, both the barrier
energy and product free energy are on the verge of the
reactant free energy (1.4 kcal mol-1 vs 0.8 kcal mol-1 vs 0
20 kcal mol-1). These calculated results indicate that compared
to 1, the single proton transfer reaction of 2 is easier to
occur, and 2 is more inclined to obtain an enol-keto mixture
while 1 not. A closer analysis of structures, we can see both Fig 4 UV-Vis absorption spectra of 1 and SA (a) as well as 2 and
60 NA (b) in methanol at room temperature, path length 1.0 cm,
the structures of reactants and transition states of 1 and 2 concentration 1×10 -5 M for each sample.
25 exist different while the product states are similar. For
Table 3 Spectral parameters of 1 and 2 in different solvents.
reactant state, the distance of N-H hydrogen-bond of
reaction center in 1 is larger than that in 2, indicating that Solvent ET(30)a λabs Log λem Φflb
(kcal mol-1) (max/nm) (εmax) (max/nm)
the proton transfers from O atom to N atom is more relaxed
1 MeOH 55.4 499 4.92 512 0.38
in 2. For TS, the distance of N-H and O-H are equivalent in CH3CN 45.6 498 4.93 511 0.48
30 2 while in 1 the distance of O-H is larger than that of N-H, THF 37.4 501 4.95 515 0.53
indicating that the structure of TS is similar to the structure CH2Cl2 40.7 502 4.95 516 0.55
toluene 33.9 505 4.92 518 0.57
of product state in 1 and to some extent means that the 2 MeOH 55.4 499 4.93 513 0.05
proton-tranfer-distance from reactant to TS in 1 is longer CH3CN 45.6 498 4.94 512 0.03
than that in 2. Therefore, the single proton transfer reaction THF 37.4 501 4.95 516 0.30
CH2Cl2 40.7 502 4.95 516 0.27
35 of 2 is easier to occur. The reason of this result may owe to toluene 33.9 505 4.96 519 0.40
the redundant benzene ring of 2 which could increase the a
Solvent polarity index. b1,3,5,7-tetramethyl-8-phenyl-BODIPY was
conjugative effect and resonant structure compared to 1 (Fig. used as a standard (Φfl = 0.72 in tetrahydrofuran).
S6 of ESI†). 65 Dyad 2 also shows an intense absorption band centered at 499
Table 2 Calculated energies, dipole moments, and frontier orbital nm with absorption coefficient around 7.97×104 M-1 cm-1. In
40 energies in vacuum and in methanol for 1-2 and their tautomers. addition, 2 displays a shoulder at the short wavelength (high-
Tautomer ETOTAL EHOMO ELUMO µ (D) energy) side, is centered at about 469 nm, and is attributed to
(hartree) (eV) (eV)
the 0-1 vibrational band of the same transition. The moderate
Gas phase 1-enol -1469.54123405 -5.6793 -2.7007 4.8157
(ε =1) 70 higher-energy transitions of NA unit in 2 were observed at 315
1-keto -1469.53340411 -5.7579 -2.7884 3.8781 and 375 nm, attributed to π-π* transition of enol form of NA.
2-enol -1623.18996163 -5.6602 -2.6814 5.4163 Interestingly, an absorption band at 438 nm was observed in the
2-keto -1623.18870347 -5.7209 -2.7483 4.4635
CH3OH 1-enol -1469.55686104 -5.8172 -2.8177 6.7180 spectrum of 2 in CH3OH, which may belong to the keto form of
(ε = 32.7) ortho-hydroxy Schiff bases.20 In contrast, any band belonging to
1-keto -1469.55389163 -5.8317 -2.8398 5.5145 75 keto-enamine form in 1 was not observed with a value greater
2-enol -1623.20631485 -5.8143 -2.8145 7.2598
2-keto -1623.20871348 -5.8153 -2.8313 5.9880 than 400 nm. Referring to previous studies it was concluded that
2 exists in both enol and keto form in CH3OH while 1 is in
2.4. Photophysical properties favor of the enol state and not in keto in most organic solvents
The optical properties of 1 and 2 were first characterized by at room temperature.8a,21 The keto form is important in the
using UV-vis absorption in solvents of varying polarity (Table 3 80 solution and stabilized by the polar solvents through solute-
and Fig. S7 of ESI†). Fig. 4 shows the absorption spectra of 1 solvent interactions. Here hydrogen bonding between hydroxyl
45 and 2 as well as references SA and NA in CH3OH. The group of methanol and nitrogen atom of Schiff base has played

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a crucial role in the proton transfer process. It can be noted that 45 1%.10e The quenching phenomenon has all the hallmarks of
in these dyads there is not any significant absorption band photoinduced electron transfer (PET) from the phenylamino
which can not be assigned to specific individual subunits: this unit to the boradizaindacene fluorophore. Upon condensation
suggests that the interaction among the various components is with salicydehyde to form 1, the reduction potential of the non-
5 weak and attachment of the Schiff base fragment to the bonding electron pair on nitrogen atom decreased due to the
BODIPY entity causes minimal perturbation of its optical 50 formation of an imine functional group. In other words, electron
properties, so that these dyads can be regarded as transfer from the electron-deficient imine moiety to the
multicomponent systems. electron-rich BODIPY fluorophore became less feasible.
Frontier orbital diagram also indicates that the highest occupied
molecular orbital (HOMO) energy of phenylamino unit (-5.38
55 eV) was higher than the HOMO energy of imine (-6.26 eV),
thereby preventing PET quenching of the emission, exhibiting
the photoluminescence quantum efficiencies vary between 0.57
and 0.38 (Table 3).

Fig 5 (a) Absorption spectra and (b) fluorescence spectra (λex = 470 nm)
10 of 2 in toluene-methanol mixtures with volume ratios of toluene; (c)
photographs of the solutions of 2 in a mixture of methanol-toluene
solvent system with different toluene fraction taken under UV
illumination.

For a better understanding of the experimental data on the

15 optical properties, the optimizations of both keto and enol forms
of 1 and 2 were carried out with the B3LYP/6-31+G(d,p) level
using polarizable continuum model (PCM) in the presence of
methanol (ε = 32.7) (Table 2). Our theoretical results allow the
conclusion that the total energy of the enol form of 1 obtained
20 by PCM method is still more stable than the keto form, though
both HOMO and LUMO energy values become more and more
negative in going from gaseous phase to solution phase with the
increase of dielectric constant value. However, calculated
energies of 2 in methanol show that the enol-imine form is less Fig 6 Proposed proton-coupled photoinduced electron transfer (PCPET)
60 mechanism between BODIPY moiety and keto unit of 2.
25 stable than the keto-enamine form by 6.30 kJ mol-1, which
indicate that it is energetically favorable to have carbon-carbon In contrast, for 2, the value of Φfl is up to 0.40 in toluene,
double bonds rather than carbon-nitrogen double bonds. In other and declines to only 0.05 in methanol. We speculate that the
words, the process of intramolecular proton transfer evoked by marked difference in fluorescence quantum yields between 1
the influence of solvent results in destabilization of the OH form and 2 in pure methanol is consistent in the prototropic
30 (a decrease in the prevalence of the OH form and an increase in 65 tautomerism, and derives from an increase in keto form for 2
that of the NH form) and destabilization of aromatic formation. compared with that of its analog 1. In order to
Thus, keto-enamine form of 2 is much more stable than enol- experimentally strengthen the above speculation, the photo-
imine, which accounts for available UV-Vis experimental physical properties of 2 had been studied in a mixture of
results. methanol-toluene, in which the toluene content (ftoluene) was
35 Steady-state fluorescence spectra of 1 and 2 were also 70 varied in the range of 0-100 vol%. The UV-Vis spectra of 2
measured in various solvents with increasing polarity from in the methanol-toluene solvent system showed several
toluene to methanol, and the details data are gathered in Table 2 isosbestic points at 410, 364, and 324 nm, which definitely
and Fig. S9 (ESI†). From the viewpoint of fluorescence, the point out the existence of two molecular absorbing species in
structures of BODIPY-linked Schiff bases can be composed of equilibrium (Fig. 5a). The luminescent properties of 2 were
40 two fragments, the BODIPY moiety as a fluorophore and Schiff 75 also investigated in the methanol-toluene system and the
base moiety as a fluorescence switch, which modulates the results are given in Fig. 5b. The emission intensity of 2
fluorescence quantum yield (Φfl) of the fluorophore, since they increased dramatically as the fraction of toluene ftoluene
are orthogonal to each other. The starting material 3 was increased, and the logarithm of the intensity and the fraction
reported to display quenched emission in methanol with Φfl < have a good linear relationship with R2 > 0.99 as shown in

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the inset of Fig 5b. The visual emission color of 2 in the The calculated frontier molecular orbital (FMO) energies and
methanol-toluene system when excited at a hand-held 365 surfaces of 2 are shown in Fig. 7. As can be found, both the
nm UV lamp is shown in Fig 5c, which is consistent with the 35 contours of the electronic distribution in HOMO and LUMO
above analysis. Overall, these findings of fluorescence states of 2 in the enol form are located almost completely on the
5 contrast with the above observations of UV-Vis spectra. BODIPY moiety, while the HOMO-1 and LUMO+1 are located
Therefore, 1 retains a moderate fluorescence quantum yield mainly on the NA fragment. It is postulated that the HOMO-
while the lower value of Φfl for 2 indicates a highly efficient LUMO transition corresponds to the emissive π→π* excited
fluorescence quenching by a thermodynamically allowed 40 state as observed in the reference dye TM-BODIPY and other
proton-coupled photoinduced electron transfer (PCPET) BODIPY derivatives.10 As a result, the electronic transition
10 from the keto unit of NA to the singlet excited state of the between HOMO and LUMO for 2 in the enol form is limited
BODIPY moiety. only on the BODIPY moiety, leading to an intensive intrinsic
To shed light on the photoinduced activation of an fluorescence from the BODIPY moiety of 2 in the enol form.
electron transfer process within an azomethine-BODIPY 45 By contrast, the calculation results reveal that both the LUMO
dyad, computations on the 1 and 2 before and after and HOMO-1 orbitals for 2 in the keto form are mostly
15 prototropic tautomerism are also performed and displayed in contributed from the BODIPY moiety, while the HOMO and
Fig. S10 (ESI†) and Fig. 6. As shown in Fig. 6, before LUMO+1 orbitals are mainly located at the NA fragment. The
prototropic tautomerism of 2, the HOMO energy level of significant distribution difference between HOMO and LUMO
enol form of NA moiety (-6.26 eV) is obviously lower than 50 of 2 in the keto form shows that there is electron transfer from
that of the BODIPY unit (-5.78 eV); therefore, the PET the NA fragment (keto form) to the BODIPY core. And this is
20 process can be suppressed and the emission of BODIPY likely related to the PET process between the NA fragment
fluorophore is on. The energy level of HOMO (-5.56 eV) of (keto form) and BODIPY core, which quenches the
keto form of NA moiety should increase above that of the fluorescence of BODIPY component.
HOMO (-5.78 eV) of the fluorophore BODIPY only after
55 2.5. Dyad 1 as ′on-off′ fluorescent chemosensor for Cu2+
prototropic tautomerism. Under these conditions, the
25 electron transfer process becomes exoergonic and favorable. Dyad 1 was preliminarily chosen to detect metal ions based on
As a consequence, when the BODIPY moiety of 2 is the following considerations: (1) as described in the foregoing
photoexcited, one electron can be transferred from the keto discussion, 1 in the enol-imine state is the most stable form at
form of NA to the BODIPY moiety with a concomitant room temperature in solution and shows moderate fluorescence
fluorescence quenching. 60 quantum yields in most medium compared to dyad 2. (2) Schiff
bases are well known to be good ligands for metal ions, and
Schiff bases incorporating a fluorescent moiety are appealing
tools for optical sensing of metal ions.22
Initially, the absorption and fluorescence response of 1
65 toward the nitrate salts of Cu2+, Ag+, Al3+, Ca2+, Co2+, Cr3+, Fe3+,
Li+, Mg2+, Mn2+, Na+, Ni2+, Pb2+, and Zn2+ were carried out in a
MeOH/CHCl3 (20:1, v/v) solution (Fig. 8a and Fig. S11).
Changes of the fluorescence properties of 1 caused by various
metal ions were measured once emission intensity was constant.
70 When 1 equiv. of Cu2+ was added to the solution of 1, the
fluorescent intensity will be reduced by 80%, which suggested
that 1 showed a particular response to Cu2+ ions compared to
those of other metal ions of similar electronic structure. It is
well-known that the paramagnetic Cu2+ center has a pronounced
75 quenching effect on fluorophores through a photoinduced
electron or energy transfer mechanism.23 Additionally, among
the relevant paramagnetic metal ions, Cu2+ has a particularly
high thermodynamic affinity for ligands with N or O as
chelating element, and fast metal-to-ligand binding kinetics
80 process.24
Selectivity is a matter of necessity for a chemosensor. To
investigate the selectivity of 1 for Cu2+ over other relevant
cations, the fluorescent intensity changes upon addition of
various competitive cations were examined, 3 equiv. of most
85 other metal ions showed no interference to the sensing of Cu2+
30 Fig 7 Molecular orbital surfaces and energy levels given in parentheses
for LUMO+1, LUMO, HOMO, and HOMO-1 of enol and keto form of by 1. Additionally, to explore the effects of anionic counterions
2 computed at the B3LYP/6-31+G(d,p) in methanol solvent. on the sensing behavior of 1 to metal ions, fluorescence

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responses of 1 to chloride, nitrate, perchlorate and sulfate salts but also presents the proton tautomerization can be designed to
with Cu2+ were examined and it can be seen that anions had no regulate the emission of an organic chromophore between a
influence on the fluorescence of 1 (Fig. S12). The fluorescence nonemissive state and an emissive one. In addition, in view of
intensity of 1 exhibits gradual reduction upon the addition of 0- 50 ortho-hydroxy aromatic Schiff bases exhibiting the interesting
5 1.0 equiv of Cu2+ and saturation upon the addition of 1.0-3.0 phenomena of photochromism,25 the detailed investigation of
equiv of Cu2+, revealing that the stoichiometry of the complex the relationship between fluorescence modulation and
formed between 1 and Cu2+ ions is 1:1 (Fig. 8b). Overall, photochromic behavior of these azomethine-BODIPY dyads as
current preliminary experiments revealed that 1 can be well as other BODIPY-linked Schiff bases both in solution and
potentially used as a simple fluorescent chemosensor which 55 in the solid state when exposed to light of different wavelengths
10 exhibited high selectivity for Cu2+ over other common cations. is under progress in our laboratory.
To further confirm the quenching mechanism, the coordination
environment of the 1/Cu2+ complex and the corresponding 4. Experimental
association constant (K), more experiments including Job’s 4.1. Materials
method, ESI-MS, X-ray crystallography and NMR titration as
15 well as DFT calculations are currently in progress. All the materials for the syntheses were purchased from
60 commercial suppliers and used without further purification. Air-
and moisture-sensitive reactions were carried out under a
nitrogen atmosphere using oven-dried glassware. Solvents were
dried by standard literature methods26 before being distilled and
stored under nitrogen over 3Å molecular sieves prior to use.
65 Water was deionized. Thin-layer chromatography (TLC) was
performed using silica gel plates and flash column
chromatography was conducted over silica gel (200-300
meshes) with the eluent reported in parentheses, both of which
were obtained from the Qingdao Ocean Chemicals.
Fig 8 (a) Emission spectra of 1 (1.0×10-5 M) in the solution of
MeOH/CHCl3 (20:1, v/v) upon addition of 3 equiv of different metal 70 4.2. Instrumentation
nitrate salts; (b) fluorescent spectra of 1 (1.0×10-5 M, excited at 470 nm)
upon addition of 0-1.0 equiv of Cu2+. 1
H and 13C NMR spectra were recorded at room temperature
using a Bruker PLUS 400 spectrometer with tetramethylsilane
20 3. Conclusions (TMS, 0.00 ppm) as an internal standard and CDCl3 as solvent.
Chemical shift multiplicities are reported as s = singlet, d =
Two new dyads made of azomethine and BODIPY subunits,
75 doublet, and br = broad singlet. Coupling constants (J) values
1-2, have been prepared, together with their parent species SA,
are given in Hz. Mass spectrometry (MS) experiment was
NA and TM-BODIPY, and the photophysical properties of all
carried out in the positive ion made on a Bruker Esquire HCT
the compounds have been investigated in fluid solution. Weak ion trap mass spectrometer (Billerica, MA) coupled with a
25 electronic interactions between Schiff base units and BODIPY homemade electrospray ionization (ESI) device. Parameters of
fragments take place in the ground states of the two dyads, 80 the ESI source were optimized to enhance the signal intensity.
whose absorption spectra resemble those of their constituting The pressure of nebulizing nitrogen, the flow rate of desolvation
groups. The marked difference in luminescence between 1 and 2 gas, and the temperature of desolvation gas were set to 8 psi, 1L
in methanol is observed and obviously consistent in the min-1, and 250 ºC, respectively. Electrochemical experiments
30 prototropic tautomerism of 2. Irradiation of the dyad 2 in the were performed using a three-electrode system. The working
enol state excites the BODIPY component, which then returns 85 electrode was 2 mm Pt with a Pt wire as auxiliary electrode and
to its ground state by emitting light in the form of fluorescence. a 0.01M Ag/AgNO3 solution reference electrode. The sample
However, the keto state of 2 can donor an electron to the excited solution contained an azomethine-BODIPY (1.0×10-3 M) and
fluorophore. As a result of the proton-coupled photoinduced 0.1 M tetrabutylammonium hexafluorophosphate (TBAP) as a
35 electron transfer (PCPET) process, the excited state of the supporting electrolyte in dry acetonitrile. FT-IR spectra were
BODIPY component is quenched and the associated 90 recorded from KBr pellet in the range 4000-400 cm-1 on a
fluorescence suppressed. Theoretical calculations of total Nicolet AVATAT FT-IR360 spectrometer. C, H, and N
energies, potential energy surface (PES) and intrinsic reaction microanalyses were carried out with a CE instruments EA 1110
coordinate (IRC) analysis also support single proton transfer analyzer. The experimental powder X-ray diffraction patterns
40 reaction from enol form to transition state (TS) and from the TS were measured on a Panalytical X-Pert Pro diffractometer with
to keto form for 2 is easier to occur than that of 1, which 95 Cu Kα radiation equipped with an X’Celerator detector.
Differential scanning calorimetry (DSC) data were measured on
accounts for the fluorescence quenching phenomenon of 2.
a Netzsch-DSC-200F3 instrument at the heating rate of 10 ºC
Additionally, 1 was preliminarily chosen as on/off type of
min-1 from 25 to 310 ºC. Samples were heated in open
fluorescent chemosensor for Cu2+ over other common cations.
aluminum pans under a nitrogen gas flow of 20 mL min-1.
45 This contribution not only attempts to integrate fluorescent
and tautomeric components within the same molecular skeleton,

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4.3. Spectroscopic measurements and determination of 78 ºC in 50 mL of absolute ethanol. When TLC analysis showed
fluorescent quantum yields that the reaction was complete, the solution was cooled to room
60 temperature. The product was collected by filtration as a red
Azomethine-BODIPYs were dissolved in various solvents to
solid. Recrystallization from CH2Cl2/EtOH (356 mg, 75% yield);
acquire optical measurements. Acetonitrile, methanol,
M.p. = 299 ºC. vmax(KBr pellet) cm-1: 3442 (νOH), 1626 (νC=N),
5 tetrahydrofuran, dichloromethane and toluene were all
1600, 1576, 1548, 1511, 1466, 1408, 1359, 1309, 1257, 1201,
individually used in preparing a BODIPY solution. UV-vis
1155, 1117, 1091, 1073, 1038, 983, 893, 829, 803, 767, 744,
absorption and steady-state fluorescence spectroscopic studies
65 707, 506, 477. 1H NMR (400MHz, CDCl3): 1.50 (s, 6H), 2.60
are performed on a UV-2100 (Shimadzu) spectrophotometer
(s, 6H), 6.03 (s, 2H), 7.26 (d, J = 9.2 Hz, 1H), 7.41 (t, J = 7.7
and a F-7000 (Hitachi) spectrophotometer at room temperature.
Hz, 3H), 7.58 (dd, J = 17.0, 7.9 Hz, 3H), 7.78 (d, J = 7.9 Hz,
10 The slit width was 5 nm for both excitation and emission.
1H), 7.89 (d, J = 9.2 Hz, 1H), 8.19 (d, J = 8.4 Hz, 1H), 9.48 (s,
Samples for absorption and emission measurements were
1H).
contained in 1 cm × 1 cm quartz cuvettes. Measurements were
70 . 13C NMR (100 MHz, CDCl3): δ 14.62, 14.70, 74.34, 76.68,
made using optically dilute solutions after deoxygenation by
77.00, 77.21, 77.32, 112.28, 116.48, 121.56, 121.87,126.17,
purging with dried N2.
127.82, 128.49, 129.17, 129.46, 130.92, 132.96, 135.60, 140.29,
15 The relative fluorescence quantum yields (Φflsample) of the
148.04, 156.01. ESI-MS m/z (C30H26BF2N3O) calculated: 493.4,
samples were obtained by comparing the area under the
found: 516.3 (M+Na), 532.3 (M+K).
corrected emission spectrum of the test sample with that of a
75 Synthesis of 8-(1-azastyryl(2-hydroxybenzaldehyde))-4,4-
standard. Only dilute solutions with an absorbance below 0.1 at
difluoro-1,3,5,7-tetramethyl 4-bora-3a,4a-diaza-s-indacene
the excitation wavelength λex were used. The Φflsample values
(1). 3 (339 mg, 1 mmol) and 2-hydroxy-1-benzaldehyde (125
20 were calculated using synthesized 8-phenyl-4,4-difluoro-
mg, 1 mmol) were refluxed for 6 h under nitrogen atmosphere at
1,3,5,7-tetramethyl 4-bora-3a,4a-diaza-s-indacene (compound 3,
78 ºC in 50 mL of absolute ethanol. When TLC analysis showed
Φflstandard = 0.72 in tetrahydrofuran)27 as fluorescence standard
80 that the reaction was complete, the solution was cooled to room
using the following equation:
temperature. The product was collected by filtration as an
Φflsample = Φflstandard × (Isample/Istandard) × (Astandard/Asample) ×
orange solid. Recrystallization from CHCl3/EtOH (300 mg,
25 (nsample/nstandard)2
80% yield); M.p. = 288 ºC. vmax(KBr pellet) cm-1: 3441 (νOH),
Where Φflsample and Φflstandard are the emission quantum yields
1623 (νC=N), 1597, 1573, 1545, 1508, 1467, 1409, 1365, 1306,
of the sample and the reference, respectively, Astandard and Asample
85 1279, 1195, 1154, 1120, 1086, 1052, 978, 910, 842, 810, 761,
are the measured absorbances of the reference and sample at the
708, 665, 581, 479. 1H NMR (400MHz, CDCl3): δ 1.48 (s, 6H),
excitation wavelength, respectively, Istandard and Isample are the
2.59 (s, 6H), 6.03 (s, 2H), 7.00 (t, J = 7.5 Hz, 1H), 7.10 (d, J =
30 area under the emission spectra of the reference and sample,
8.2 Hz, 1H), 7.39 (d, J = 8.3 Hz, 2H), 7.41-7.49 (m, 4H), 8.74 (s,
respectively, and nstandard and nsample are the refractive indices of
1H), 13.08 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 14.75,
the solvents of the reference and sample, respectively. The
90 14.64, 76.71, 77.02, 77.23, 77.34, 117.40, 119.03, 119.29,
Φflsample values reported in this work are the averages of multiple
121.35, 122.00, 129.09, 129.32, 131.46, 132.51, 133.58, 133.66,
(generally three), fully independent measurements.
140.95, 143.00, 149.10, 155.71, 161.26, 163.45. ESI-MS m/z
35 4.4. Synthetic procedures (C26H24BF2N3O) calculated: 443.3, found: 466.3 (M+Na), 482.3
(M+K).
The syntheses of the starting BODIPY compounds NH2-
95 8-phenyl-4,4-difluoro-1,3,5,7-tetramethyl 4-bora-3a,4a-
BODIPY (3) and NO2-BODIPY (4) were achieved using
diaza-s-indacene (5) was synthesized according to the literature
literature methods and characterized by 1H NMR, 13C NMR and
reports.15 1H NMR (400 MHz, CDCl3) δ 1.39 (s, 6H, CH3), 2.58
elemental analysis to determine their structures.10e,12
(s, 6H, CH3), 6.00 (s, 2H), 7.28-7.32 (m, 2H, phenyl), 7.49-7.50
40 8-(4-nitro-phenyl)-4,4-difluoro-1,3,5,7-tetramethyl 4-bora-
(m, 3H, phenyl); 13C NMR (100 MHz, CDCl3) δ 14.3, 14.6,
3a,4a-diaza-s-indacene (4):. 1H NMR (400 MHz, CDCl3) δ
100 121.2, 127.9, 128.9, 129.1, 131.4, 135.0, 141.7, 143.1, 155.4.
1.37 (s, 6H), 2.57 (s, 6H), 6.03 (s, 2H), 7.54 (d, 2H, J = 8.8 Hz),
Anal. Cacld for C19H19BF2N2: C, 70.40; H, 5.91; N, 8.64.
8.39 (d, 2H, J = 8.8 Hz); 13C NMR (100 MHz, CDCl3) δ 14.5,
Found: C, 70.44; H, 5.88; N, 8.67. Since 5 is one internal
121.7, 124.4, 129.6, 130.6, 138.3, 141.9, 142.5, 148.4, 156.3.
reference dye for the determination of quantum yields and it is
45 Anal. Cacld for C19H18BF2O2N3: C, 61.81; H, 4.91; N, 11.38.
regularly checked for stability and purity.
Found: C, 61.78; H, 4.87; N, 11.35.
105 4,4-difluoro-1,3,5,7-tetramethyl 4-bora-3a,4a-diaza-s-
8-(4-amino-phenyl)-4,4-difluoro-1,3,5,7-tetramethyl 4-bora-
indacene (the model TM-BODIPY) was prepared using a
3a,4a-diaza-s-indacene (3):. 1H NMR (400 MHz, CDCl3) δ
literature procedure.19 13C NMR (125 MHz, CDCl3) δ 11.3, 14.6,
1.51 (s, 6H), 2.57 (s, 6H), 4.44 (br, 2H), 5.99 (s, 2H), 6.86 (d,
119.1, 120.2, 133.3, 141.2, 156.7. ESI-MS m/z (C13H15BF2N2)
50 2H, J = 4.0 Hz), 7.05 (d, 2H, J = 6.8 Hz); 13C NMR (150 MHz,
calculated: 248.1, found: 271.1 (M+Na).
CDCl3) δ 14.5, 14.6, 115.5, 119.7, 120.9, 124.7, 128.8, 128.9,
110 References N-salicylideneaniline (SA) and N-
132.0, 142.6, 143.2, 146.9, 154.9. Anal. Cacld for C19H20BF2N3:
naphthlideneaniline (NA) are synthesized by the appropriate
C, 67.28; H, 5.94; N, 12.39. Found: C, 67.33; H, 5.91; N, 12.31.
condensation of the corresponding aldehyde and aniline
Synthesis of 8-(1-azastyryl(2-hydroxynaphthaldehyde))-4,4-
according to the standard procedures as previously reported.8c,28
55 difluoro-1,3,5,7-tetramethyl 4-bora-3a,4a-diaza-s-indacene
Pure SA and NA obtained after recrystallization twice from
(2): 3 (339 mg, 1 mmol) and 2-hydroxy-1-naphthaldehyde (172
115 absolute ethanol. The melting points agreed with those in the
mg, 1 mmol) were refluxed for 6 h under nitrogen atmosphere at

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literature and the elemental analyses were in accord. Other transition states (TS) of 1 and 2 in gas phase is performed by
analysis data are as follows. SA: M.p. 51-53ºC. 1H carrying out density functional theory (DFT) calculations with
NMR(400MHz, CDCl3): δ 6.98 (q, 1H, J = 7.3 Hz), 7.09(d, 1H, Becke’s three-parameter exchange and Lee-Yang-Parr
J = 8.3 Hz), 7.33 (m, 3H), 7.45 (m, 4H), 8.67 (s, 1H). FT-IR 60 correlation functionals (B3LYP) with a combination of 6-
5 transmission (KBr pellet): 3433 cm-1 (νOH), 1615 cm-1 (νC=N), 31+G(d,p) basis set. The harmonic vibrational frequencies of
1590, 1572, 1507, 1496, 1485, 1453, 1402, 1361, 1277, 1186, the studied structures are calculated at the same level to
1169, 1150, 1116, 1074, 1032, 982, 917, 896, 843, 780, 757, characterize their existence on the potential energy surface
691, 547, 523 cm-1. UV-Vis, λmax/nm, (ε/L mol-1 cm-1), (PES). The minimum energy structures are ensured by the
(CH3OH): 269 nm (11000), 348 nm (10570). Anal. Cacld for 65 absence of any imaginary frequency whereas any transition state
10 C13H11NO (197.23): C, 79.17; H, 5.62; N, 7.10. Found: C, is characterized by the presence of only one imaginary
79.12; H, 5.57; N, 7.02. NA: M.p. 95-97ºC. 1H NMR(400MHz, frequency. In solution phase, the geometry optimization of the
CDCl3): δ 7.14 (d, 1H, J = 9.12Hz), 7.37(d, 2H, J = 8.52Hz), studied structures is performed at the same level with
7.44 (m, 2H, J = 13.48Hz), 7.71 (d, 1H, J = 7.93Hz), 7.80 (d, polarizable continuum model (PCM). All molecular orbitals
1H, J = 9.11Hz), 8.07(d, 1H, J = 8.59Hz). FT-IR transmission 70 were visualized with the software GaussView 5.0.
15 (KBr pellet): 3437 cm-1 (νOH), 1626 cm-1 (νC=N), 1570, 1542,
1489, 1476, 1420, 1329, 1248, 1181, 1163, 1076, 1023, 967, Acknowledgements
911, 873, 824, 750, 694 cm-1. UV-Vis, λmax/nm, (ε/L mol-1 cm-1),
(CH3OH): 315 nm (17283), 357 (12228), 435 nm(22000) and This work was financially supported by the National Natural
455 nm(20400). Anal. Cacld for C17H13NO (247.3): C, 82.57; Science Foundation of China (no. 21201066), the Natural
20 H, 5.30; N, 5.66. Found: C, 82.61; H, 5.35; N, 5.55. Science Foundation of Fujian Province (no. 2011J01047), the
75 outstanding Youth Scientific Research Cultivation Plan of
4.5. Crystallization experiments and X-ray crystallography Colleges and Universities of Fujian Province (JA13008), and
The quality of single crystals depends on the purity of the Promotion Program for Young and Middle-aged Teacher in
used material. Hence, the synthesized target dyads were highly Science and Technology Research of Huaqiao University
purified (recrystallization at least twice before performing (ZQN-PY104). Dr. Hai-Feng Su (Xiamen University) is greatly
25 crystallization experiments). Better quality crystals of 1 and 2 80 acknowledged for assistance with the ESI-MS experiments and
were obtained by slow vapour diffusion of n-hexane into a we thank Dr. Hong-Xin Mei (Xiamen University) for help with
saturated CHCl3 solution of 1 or CH2Cl2 solution of 2 at room the single-crystal X-ray diffraction data collections. Zhong-Hua
temperature. Pan also thanks the National Innovative Foundation Project for
Intensity data for 1 and 2 were collected on a Rigaku R-AXIS undergraduates (no. 201310385004).
30 RAPID Image Plate single-crystal diffractometer using
graphite-monochromated Mo Kα radiation source (λ = 0.71073 85 Notes and references
Å). Single crystals of 1 and 2 with appropriate dimensions were
(1) J. Toullec, Adv. Phys. Org. Chem., 1982, 18, 1-261.
chosen under an optical microscope and mounted on a glass (2) (a) S. K. Pollack and W. J. Hehre, J. Am. Chem. Soc., 1977, 99,
fiber for data collection at low temperature (173 ± 2K). 4845-4846; (b) H. E. Zimmermann, Acc. Chem. Res., 1987, 20,
35 Absorption correction was applied by correction of symmetry- 263-268; (c) J. Toullec and J. E. Dubois, J. Am. Chem. Soc., 1974,
equivalent reflections using the ABSCOR program.29 All 90 96, 3524-3532.
(3) (a) R. Glaser and M. Lewis, Org. Lett., 1999, 1, 273-276; (b) R. S.
structures were solved by direct methods using SHELXS-9730 Phillips, B. Sundararaju and N. G. Faleev, J. Am. Chem. Soc.,
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( Ropt − Ri ) 2 ,
i =1
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70 5607.

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 Physical Chemistry Chemical Physics Page 12 of 12

Physical Chemistry Chemical Physics Accepted Manuscript

Graphical Abstract
Enol↔keto prototropic tautomerism can be exploited to modulate the photophysics of BODIPY chromophores based
on proton-coupled photoinduced electron transfer processes.

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