ARTICLE

pubs.acs.org/IC

3,5-Diformylboron Dipyrromethenes as Fluorescent pH Sensors

Sheri Madhu,† Malakalapalli Rajeswara Rao,† Mushtaque S. Shaikh,‡ and Mangalampalli Ravikanth*,†
†
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India
‡
Department of Pharmaceutical Chemistry, Bombay College of Pharmacy, Santacruz (E), Mumbai 400 098, India

bS Supporting Information
ABSTRACT: A series of boron dipyrromethene (BODIPY)
dyes containing two aldehyde functional groups at the 3 and 5
positions have been synthesized in low-to-decent yields in two
steps. In the first step, the meso-aryl dipyrromethanes were
treated with POCl3 in N,N-dimethylformamide to afford 1,9-
diformylated dipyrromethanes. In the second step, the difor-
mylated dipyrromethanes were first in situ oxidized with 2,3-
dichloro-5,6-dicyano-1,4-benzoquinone and then reacted with
BF3 3 OEt2 to afford 3,5-diformylboron dipyrromethenes. The X-ray structural analysis indicated that the aldehyde groups are
involved in intramolecular hydrogen bonding with fluoride atoms, which may be responsible for the stability of the diformylated
BODIPY compounds. The presence of two formyl groups significantly alters the electronic properties, which is clearly evident in
downfield shifts in the 1H and 19F NMR spectra, bathochromic shifts in the absorption and fluorescence spectra, better quantum
yields, and increased lifetimes compared to 3,5-unsubstituted BODIPYs. Furthermore, 3,5-diformylboron dipyrromethenes are
highly electron-deficient and undergo facile reductions compared to unsubstituted BODIPYs. These compounds exhibit pH-
dependent on/off fluorescence and thus act as fluorescent pH sensors.

’ INTRODUCTION group can be used as a fluoresecent pH sensor. In this paper, we

Fluorescent chemosensors that are responsive to changes in report a simple route for the synthesis of 3,5-diformylboron
the pH are widely used in analytical chemistry, physiology, and dipyrromethene dyes and demonstrate their use as fluorescent
biosciences.1 The fluorescence method offers several advantages pH sensors. Because the electron-withdrawing aldehyde groups
over other methods for physiological pH measurements because are placed directly in conjugation with electron-rich BODIPY,
of its high sensitivity. There are a wide range of fluorescent these compounds are sensitive toward the pH and act as
indicator dyes that can sense pH changes.1 In recent years, a lot fluorescent pH sensors. While we designed this project, Sathya-
of work has been focused on the synthesis of 4,4-difluoro-4- moorthi et al.9a and recently Ziessel et al.9b reported the synthesis
bora-3a,4a-diaza-s-indacene-based2 (boron dipyrromethene or of BODIPYs having a formyl group at the 3 position by 2,3-
BODIPY3) fluorescent probes and their application4 as selective dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation of
and efficient sensors of ionic species. BODIPY dyes possess corresponding 3-methylboron dipyrromethenes (Scheme 1a).
excellent qualities such as high photostability, high fluorescence Furthermore, while our work was in progress, Jiao et al.10
quantum yields, narrow emission band widths, relatively high reported the synthesis of BODIPYs containing a formyl group
absorption coefficients, and excitation/emission wavelengths at the 2 position by subjecting the appropriate BODIPYs to the
above 500 nm.5 It is now well established that, by simple
modified Vilsmeier
Haack conditions (Scheme 1b).
modifications on the BODIPY dye, it is possible to tune the
However, their efforts to synthesize the diformylated BODI-
absorption/emission peak maxima, which range from 500 to over
PYs under various reaction conditions remained unsuccessful,
700 nm.5 BODIPY-based fluorophores have been applied as pH
sensors in organic solvents or aqueous/organic mixed media.6
8 which they attributed to the instability of the diformylated
BODIPY dyes bearing phenolic,6 (dialkylamino)phenyl,7 and BODIPYs.10 Here we showed a different approach to synthesiz-
calix[4]arene8 subunits at meso positions have been used as pH ing the first examples of 3,5-diformylboron dipyrromethenes,
sensors, and these compounds showed deprotonation/proton- which are stable and isolated in 7
26% yield. Furthermore, we
ation-dependent fluorescence off/on switching. A perusal of the also showed the use of 3,5-diformylboron dipyrromethenes as
literature reveals that aldehyde groups are generally not used for fluorescent pH sensors, which exhibit fluorescence on and off
fluorescent pH sensors. This is because the aldehyde group states under acidic and basic pH regions, respectively.
present in the fluorophore is less sensitive toward pH variation,
unlike hydroxy/amine/carboxylate groups. However, if an alde-
hyde group is placed appropriately in conjugation with the Received: December 14, 2010
fluorophore, the fluorophore containing an aldehyde functional Published: April 21, 2011

r 2011 American Chemical Society 4392 dx.doi.org/10.1021/ic102499h | Inorg. Chem. 2011, 50, 4392–4400
Inorganic Chemistry ARTICLE

’ RESULTS AND DISCUSSION triethylamine and BF3 3 OEt2 at room temperature for 10 min.
The synthesis of 3,5-diformylboron dipyrromethenes 9
12, Thin-layer chromatographic analysis showed a fluorescent yel-
starting from their corresponding unsubstituted dipyrro- low spot of the desired compound. The crude compounds were
methanes (DPMs) 1
4, is shown in Scheme 2. The required subjected to flash silica gel column chromatographic purification
dipyrromethanes 1
4 were prepared according to Lindsey’s and afforded pure 3,5-diformylboron dipyrromethenes 9
12 as
procedure11 by condensing the appropriate aldehyde with excess green solids in 7
26% yield. It is observed that BF3 3 OEt2 should
pyrrole in the presence of a catalytic amount of trifluoroacetic be added immediately after the addition of triethylamine, and any
acid at room temperature. The DPMs were purified by flash silica time delay between the addition of these two reagents to the
gel column chromatography and afforded pure compounds reaction mixture resulted in decomposition of the compound.
1
4 as white solids in 56
76% yield. The 1,9-diformyl The molecular-ion peaks in high-resolution mass spectra con-
dipyrromethanes12 [DPM(CHO)2] 5
8 were prepared in the firmed the identity of compounds 9
12. 1H, 13C, 19F, and 11B
next step by treating DPMs 1
4 with the Vilsmeier reagent in NMR spectroscopies have been used to characterize compounds
1,2-dichloroethane at reflux temperature, followed by column 9
12 in detail. In 1H NMR, the absence of a signal at ∼7.94
chromatographic purification on silica, and afforded pure 1,9- ppm corresponding to 3,5 protons of BODIPY and the presence
diformyl dipyrromethanes 5
7 as white solids and 1,9-diformyl of a typical singlet at ∼10.5 ppm corresponding to an aldehyde
dipyrromethane 8 as a light-brown solid in 67
82% yield. proton support that formylation occurred at the 3 and 5
Compounds 5
8 were characterized by various spectroscopic positions. The comparison of the 1H, 19F, and 11B NMR spectra
techniques, and the data for known compounds 5
7 are in of 3,5-diformylboron dipyrromethene 9 with 3,5-unsubstituted
agreement with those in the literature.12 A signal at ∼10.7 ppm in BODIPY13 13 is presented in Figure 1, and relevant NMR data of
1
H NMR and a molecular-ion peak in mass spectra confirmed the compounds 9
12 along with compound 13 are presented in
identity of 1,9-diformyl dipyrromethanes 5
8. The target 3,5- Table 1. As is clear from Figure 1 and the data in Table 1, the
diformylboron dipyrromethenes 9
12 were prepared in two presence of two electron-withdrawing formyl groups at the 3 and
steps in a one-pot reaction. In the first step, the appropriate 5 positions alters the π delocalization, which is reflected in the
diformyl dipyrromethanes 5
8 were oxidized in dichloro- downfield shifts in 1H, 19F, and 11B NMR. In 1H NMR, the
methane with DDQ for 30 min, followed by treatment with β-pyrrole protons Ha and Hb, which appear as two sets of signals at
6.55 and 6.90 ppm, respectively, in compound 13,13 experienced
downfield shifts and appeared at 7.11 and 7.19 ppm, respectively,
Scheme 1. Synthesis of the Reported BODIPYs in compound 9. Compounds 10
12 also exhibited similar
downfield shifts of Ha and Hb, supporting alteration of the π
delocalization upon the introduction of two formyl groups at the
3 and 5 positions. In 11B NMR, compounds 9
12 showed a
typical triplet like compound 13. However, compounds 9
12
exhibited a 0.75 ppm downfield shift of the triplet and appeared
at 1.26 ppm, unlike compound 13, in which the triplet was
observed at ∼0.5 ppm in 11B NMR (Table 1). These kinds of
significant downfield shifts observed in 11B NMR were not very
common for BODIPYs.14 The downfield shifts observed in 1H
and 11B NMR spectra for compound 9 compared to compound
13 indicate that the strong electron-withdrawing formyl groups
make the BODIPY unit electron-deficient. The density func-
tional theory (DFT) studies discussed later also indicated that
the electron density is more toward formyl groups and the

Scheme 2. Synthesis of 3,5-Diformylboron Dipyrromethenes 9
12

4393 dx.doi.org/10.1021/ic102499h |Inorg. Chem. 2011, 50, 4392–4400

Inorganic Chemistry ARTICLE

Figure 1. Comparison of (a) 1H, (b) 11B, and (c) 19F NMR spectra of compounds 9 and 13 in selected regions recorded in CDCl3.

Table 1. 1H, 19F, and 11B NMR Data of Compounds 9
12 which the presence of internal hydrogen bonding between fluo-
along with 13 Recorded in CDCl3 ride ions and amido protons resulted in a
16 ppm downfield
1
shift of the signal in 19F NMR. Furthermore, the 1H NMR spectra
H NMR recorded for compound 9 in five deuterated solvents of varying
compound Ha Hb Hc 19
F NMR 11
B NMR polarity such as benzene, chloroform, acetone, acetonitrile, and
methanol clearly indicated that the aldehyde proton (Hc) is
13 6.55 6.90
145.4 0.50 shifted upfield by 0.6 ppm in methanol compared to benzene
9 7.11 7.19 10.478
130.8 1.26 (Figure S26 in the Supporting Information). Similar observa-
10 7.07 7.20 10.476
130.8 1.24 tions were made in 19F NMR spectra recorded for 9 in deuterated
11 7.14 7.21 10.474
130.7 1.28 chloroform and methanol (Figure S27 in the Supporting In-
12 6.84 7.18 10.480
130.5 1.24 formation). In chloroform, the quartet signal in the 19F NMR
spectrum was observed downfield (
130 ppm) because of the
presence of hydrogen bonding, while in methanol, the hydrogen
BODIPY ring remains electron-deficient in compound 9. The bonding is absent, which is reflected in an upfield shift of the
most interesting observations were made in the 19F NMR spectra signal (
140 ppm). This supports the fact that the polar solvent
of compounds 9
12. In all reported BODIPYs such as 13, the breaks hydrogen bonding, whereas hydrogen bonding is stabi-
19
F NMR spectrum corresponds to a single quartet because of lized in a nonpolar solvent. The 3,5-disubstituted BODIPYs16,17
coupling to 11B (I = 3/2 and J = 32 Hz) and resonances at are the first class of compounds where intramolecular hydrogen
approximately
147 ppm.13 bonding was established crystallographically. Because we in-
However, in some recently reported BODIPY compounds,15 ferred hydrogen bonding in compounds 9
12 from the 19F
the fluorines were found to be inequvalent and showed two sets and 1H NMR study, we attempted to grow single crystals of
of multiplets at ∼
140 ppm. In complexes 9
12, we observed compounds 9
12. We successfully obtained single crystals for
only one quartet in 19F NMR, indicating that the fluorines are compound 11 by the slow evoporation of n-hexane/CHCl3 (1:1)
under a chemically equivalent environment. However, com- over a period of 1 week, which crystallized in a triclinic P1 unit
pounds 9
12 exhibited a 19F NMR signal at ∼
131 ppm, cell. The crystal structure of compound 11 is shown in Figure 2.
a
15 ppm downfield shift compared to that of the other Compound 11 has a planar BODIPY framework, which is com-
reported BODIPYs.13 This unusual downfield shift was attrib- prised of two pyrrole rings and a central six-membered boron
uted to the presence of hydrogen bonding between fluoride ions ring like that reported in meso-(phenyl)boron dipyrromethene
and an aldehyde group. This observation is in line with the compound 14 (Table S1 in the Supporting Information). The
recently reported16 3,5-diamidoboron dipyrromethene dyes, in dihedral angle between the meso-aryl ring and the BODIPY core
4394 dx.doi.org/10.1021/ic102499h |Inorg. Chem. 2011, 50, 4392–4400
Inorganic Chemistry ARTICLE

Figure 3. Comparison of the reduction waves of the cyclic voltammo-

Figure 2. ORTEP diagram (50% probability) of compound 11. grams of compounds 9 and 13 in dichloromethane containing 0.1 M
tetrabutylammonium perchlorate as the supporting electrolyte recorded
is 48°, which is closer to that of 14 (∼60°),13 indicating the at a 50 mV s
1 scan rate.
presence of free rotation of the meso-aryl group in compound 11.
The striking feature of compound 11 is the presence of intra- In addition, an ill-defined band at ∼400 nm corresponding to a
molecular hydrogen bonding between the boron-bound fluoride S0 f S2 transition is also present. The absorption bands possess
groups and the aldehyde groups present at the 3 and 5 positions narrow spectral bandwidths in compounds 9
12. These absorp-
(Table S1 in the Supporting Information). Each fluoride in tion features are in agreement with those of other BODIPY dyes
compound 11 is involved in hydrogen bonding with one of such as 13. Similarly, compounds 9
12 showed a single fluor-
the aldehyde protons with C
H 3 3 3 F distances of 2.50 Å escence band with a bandwidth comparable to that of unsub-
(C
H1 3 3 3 F1) and 2.91 Å (C
H11 3 3 3 F2). The presence of stituted BODIPY 13. However, the data presented in Table 2
two formyl groups at the 3 and 5 positions also alters the bond reveal the following differences and similarities between 3,5-
lengths and angles slightly compared to those of 14 (Table S1 in diformylboron dipyrromethenes 9
12 and 3,5-unsubstituted
the Supporting Information), which is attributed to the electron- BODIPY 13: (1) Compounds 9
12 exhibited a 40
50 nm
withdrawing nature of the formyl groups. red shift in the S0 f S1 absorption band (Figure 4a), and the
Compounds 9
12 were further characterized by cyclic vol- molar absorption coeffiecients are 2
3 times lower compared to
tammetry, steady-state absorption and fluorescence, and time- that of 13. This is due to the presence of electron-withdrawing
resolved fluorescence techniques. The electrochemical proper- formyl groups in compounds 9
12. (2) The absorption study of
ties of compounds 9
12 along with 13 were followed by cyclic compounds 9
12 in different solvents (Table S3 in the Support-
voltammetry in CH2Cl2 using tetrabutylammonium perchlorate ing Information) indicated that the absorption properties are
as the supporting electrolyte. A comparison of the reduction greatly affected by the solvent polarity. The absorption band was
waves of compound 9 with those of compound 13 is shown in blue-shifted and its intensity was reduced with an increase in the
Figure 3. Compounds 9
11 showed no oxidation waves but two solvent polarity. Thus, compounds 9
12 shows strong absorp-
reversible reductions occurring at the boron dipyrromethene tion in less polar solvents like chloroform, which is shifted to blue
unit (Table S2 in the Supporting Information). The absence of with a very weak and broad absorption in polar solvents like
oxidation in compounds 9
11 indicates the electron-deficient methanol. This is due to the prevention of conjugation between
nature of the boron dipyrromethene unit. Compound 12 showed formyl groups and the BODIPY core in polar solvents like
two oxidations at 0.81 and 1.32 V, which are due to the presence methanol, but it is operational in nonpolar solvents like chloro-
of an electron-rich 3,4,5-trimethoxyphenyl group at the meso form. Although BODIPY compounds such as 13, which does not
position. The electron-deficient nature of the boron dipyrro- have formyl groups at the 3 and 5 positions, also exhibit slight
methene unit in compounds 9
12 is clearly evident in the first hypsochromic shifts with an increase in the solvent polarity, the
and second reduction potentials, which were shifted by ∼650 mV effects observed for compounds 9
12 were quite significant. (3)
toward less negative compared to that of 13, indicating that the Compounds 9
12 showed typical emission features of BODIPY
3,5-diformylboron dipyrromethenes 9
12 are very easy to dyes, that is, narrow, slightly Stokes-shifted bands of mirror
reduce. This significant shift in the reduction potentials of image shape. The smaller Stokes shift suggests that the difference
compounds 9
12 compared to that of 13 supports the strong between the ground and excited states is much less and these
electron-withdrawing effect of the formyl groups present at the 3 BODIPYs undergo less structural reorganization in the excited
and 5 positions in 9
12 (Table S2 in the Supporting In- state, like any other reported BODIPY.18 (4) Compounds 9
12
formation). The absorption and fluorescence properties of showed bathochromically shifted emission bands compared to
compounds 9
12 were studied in different solvents of varying that of 3,5-unsubstituted BODIPY 13 (Figure 4b). (5) Com-
polarity (Table S3 in the Supporting Information), and the pounds 9 and 10 showed decent quantum yields compared to
relevant data of compounds 9
12 along with compound 13 in that of 13; compound 11 showed a lower quantum yield, and
CHCl3 are presented in Table 2. The absorption spectra of compound 12 was completely nonfluorescent. The poor fluor-
compounds 9
12, in general, showed a characteristic strong escence behavior of compounds 11 and 12 is due to electron-rich
band corresponding to a S0 f S1 transition in the 540
550 nm meso-aryl groups that are involved in photoinduced electron
region with one vibronic component on the higher energy side. transfer (PET) with the BODIPY core. (6) The fluorescence
4395 dx.doi.org/10.1021/ic102499h |Inorg. Chem. 2011, 50, 4392–4400
Inorganic Chemistry ARTICLE

Table 2. Photophysical Data of Compounds 9
13 Recorded in CHCl3a

compound λabs (nm) λem (nm) Δνst (cm
1) log ε Φ τ (ns) kr (109 s
1) knr (109 s
1)

13 501 517 618 4.74 0.03 0.51 0.059 1.90

9 546 556 329 4.09 0.31 5.9 0.053 0.117
10 550 560 325 3.77 0.30 5.5 0.055 0.127
11 544 554 332 4.25 0.09 1.4 0.064 0.650
12 548 570 704 4.06
a
log(ε/mol
1 dm3 cm
1)
molar extinction coefficient, λabs (absorption maxima), λem (emission maxima), Δν (Stokes shift), Φ (quantum yield), τ
(lifetime), kr (radiative decay), and knr (nonradiative decay).

Figure 4. Comparison of normalized (a) absorption and (b) emission spectra of compounds 9 (—) and 13 (---) recorded in chloroform.

band of compounds 9
11 was hypsochromically shifted and

quantum yields were decreased with an increase in the polarity of
the solvent (Table S3 in the Supporting Information). These
observations were in agreement with the general behavior of
other BODIPYs. Thus, the steady-state absorption and fluores-
cence study revealed that compounds 9
12 exhibit altered
properties compared to 13, which is due to the presence of
electron-withdrawing formyl groups at the 3 and 5 positions. The
time-resolved fluorescence studies were carried out in order to
understand their fluorescence properties in detail (Figure S28 in
the Supporting Information). Compounds 9
11 showed single-
exponential decay, and their singlet state lifetimes were larger
than that of compound 13. The fluorescence decay of com-
pounds 9
11 studied in different solvents also showed generally
single-exponential decay, and the lifetimes were parallel with Figure 5. Energies and electron distribution patterns in the HOMO
their observed fluorescence quantum yields (Table S3 in the and LUMO states of molecules 13 (left) and 9 (right).
Supporting Information).
To understand the basis of having distinct properties of 3,5- groups stabilize both states of BODIPY, the energy gap is just
diformylboron dipyrromethene at molecular and electronic levels, slightly less than that of molecule 13 (a difference of 0.013 eV was
ab initio calculations were carried out on compounds 9 and 13 observed). Such an effect could have arisen through extension
using the Gaussian program19a with DFT,19b the B3LYP19c of π conjugation introduced in the system and the electron-
method, and 6-31þG(d,p)19d as the basis set. The contours of withdrawing ability of the 3,5-diformyl groups. Although the
the electronic distribution in highest occupied molecular orbital HOMO
LUMO energies give a clear idea that 3,5-diformylboron
(HOMO) and lowest unoccupied molecular orbital (LUMO) dipyrromethenes are easily reducible, which is in agreement
states on these molecules suggested that there were very minute but with our experimental results, the better indicators for the redox
essential differences between compounds 9 and 13 (Figure 5). properties are electron affinity (EA) and ionization potential (IP)
Precisely, the HOMO states of the two molecules seem to be data. The EA is a fundamental property of atoms and molecules
superimposable in the BODIPY nucleus, while close examination and is defined as the energy difference between an uncharged
of the LUMO states of compounds 9 and 13 revealed that species and its negative ion.20 For both molecules 9 and 13, the
electrons were more delocalized toward the 3,5-diformyl groups negative ions were generated by defining the value of charge
in molecule 9, making the BODIPY nucleus slightly electron- as
1 and multiplicity as 2. Similarly, the IP is defined as the
deficient. It was interesting to note that, although the 3,5-diformyl amount of energy required for removing one electron from a
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Inorganic Chemistry ARTICLE

Table 3. Data Generated from the Computational Study for

Compounds 13 and 9
HOMO energy LUMO energy
molecule (eV) (eV) EA (eV) IP (eV)

13
6.1756
3.1123 1.846 7.4465

9
6.2733
3.2225 2.881 8.6381

molecule and is generally computed as the energy difference

between its cationic and neutral states.21 The cations were
generated by defining the value of charge as 1 and multiplicity
as 2 for calculations. These ions were optimized with the above-
mentioned protocol. The heats of formation were corrected for
zero point for calculation of the EA and IP data. The computa-
tional data for the two molecules are given in Table 3. It is clear
from the data that the EA for molecule 9 is higher than that for
molecule 13; i.e., molecule 9 is more reducible compared to 13.
The IPs of the two molecules indicate that molecule 9 is difficult
to oxidize. Thus, the quantum-mechanics-based studies of these
molecules were found to be in accordance with the experi-
mental data.
It is well established in the literature that BODIPYs bearing
hydroxyaryl6/diaminoaryl7/calix[4]arene8 groups at the meso
position can be used as deprotonation/protonation-dependent
fluorescence off/on pH sensors. The phenolic, N,N-dialkylani-
line, and calix[4]arene derivatives sense the alkaline, acidic, and
near-neutral pH range, respectively. The low emission intensity
of the phenolate or uncharged dialkylaniline forms has been
attributed to charge transfer from phenolate or uncharged N,
N-dialkylaniline donors to the excited-state BODIPY acceptor Figure 6. (a) Absorption spectra of compound 9 (5 μM) in an aqueous
moiety. Interestingly, the fluorophore-bearing aldehyde group is acetate buffer solution (0.1 M) as a function of the pH. (b) Fluorescence
generally not used as the fluorescent pH sensor. This is because spectra of compound 9 (5 μM) in an acetate buffer solution (0.1 M) as a
of the electron-deficient nature of aldehyde, which prevents its function of the pH. The excitation wavelength used was 488 nm. The
involvement in charge transfer with the fluorophore. However, in inset shows the plot of I/Imax vs pH.
BODIPY compounds 9
12, the aldehyde groups at the 3 and 5
positions are relatively more electron-rich because these groups
are directly involved in π conjugation of the BODIPY unit. Hence, at pH 9. However, the decrease in the emission intensity is not very
we assumed that the aldehyde groups in BODIPY compounds substantial as we move toward alkaline pH from pH 7, indicating
9
12 are as senstive as the phenolic/(dialkylamino)phenyl group that compound 9 is less fluorescent even at neutral pH. Upon a
toward the pH and can be used as fluorescent pH sensors. We decrease from pH 7 to acidic pH (pH 4), the emission intensity was
carried out systematic pH-dependent absorption studies on com- enhanced by 17 times and a maximum change was found within the
pounds 9
12 and fluorescence studies on compounds 9
11 in an pH range of 6.5
4.0 (pKa = 6.39 at pH 4).22 This is also clearly
acetate buffer solution over a pH range of 4.0
9.0 (Table S4 in the reflected in the sigmoidal response observed in the plot of I/Imax vs
Supporting Information), and the effect of the pH on the absorp- pH, where Imax is the maximum fluorescence intensity of com-
tion and fluorescence of compound 9 is shown in Figure 6. The pound 9 and I is the fluorescence intensity at a particular pH.
absorption spectra of compounds 9
12 as a function of the pH in Similar observations were made for compounds 10 and 11 (Table
an acetate buffer solution exhibited an increase of the respective S4 in the Supporting Information). However, compound 12 was
absorption bands with increasing Hþ concentration without too weakly fluorescent to perform pH titration studies and
changes in the peak maxima, as shown in Figure 6a for compound compound 13, which does not have formyl groups at the 3 and 5
9. Because the absorption studies are performed in a polar medium, positions, did not exhibit any changes in the fluorescence intensity
the absorption bands of BODIPY are already hypsochromically upon variation of the pH. These significant changes in acidic and
shifted compared to a nonpolar medium like benzene; hence, no alkaline media represent two different “states”, where the fluores-
shifts in the absorption peak maxima are expected with changes of cence is “switched off” (state I) in an alkaline solution and
the pH in the buffer medium. The emission peak maxima of “switched on” (state II) in an acidic solution, as shown in Scheme 3.
compounds 9
11 also remain unaltered in different pH solutions, In an alkaline solution, the aldehyde group is electron-rich and
but their intensities were significantly altered. For example, at pH 8, engaged in PET quenching of the BODIPY excited state, and in an
compound 9 was very weakly fluorescent. Furthermore, the acidic medium, the PET quenching is prevented because of
fluorescence switching process was also found to be reversible. It protonation of the aldehyde group. To confirm that 3,5-diformyl-
was observed that compound 9 showed some emission at pH 7, but boron dipyrromethenes exist in two different states, we recorded
1
the emission intensity decreased as the pH of the alkaline medium H NMR spectra of compound 9 at basic and acidic media (Figure
was increased and compound 9 became completely nonfluorescent S29 in the Supporting Information). NMR spectra of compound 9
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Inorganic Chemistry ARTICLE

Scheme 3. Schematic Representation of the Fluorescence steady-state fluorescence spectra were obtained with Perkin-Elmer
On/Off pH Sensor Lambda-35 and PC1 photon-counting spectrofluorometers manufac-
tured by ISS and USA Instruments, respectively. The fluorescence
quantum yields (Φf) were estimated from the emission and absorption
spectra by comparative method at the excitation wavelength of 488 nm
using Rhodamine 6G (Φf = 0.76)17a as standard. The time-resolved
fluorescence decay measurements were carried out at magic angle using
a picosecond diode-laser-based time-correlated single-photon-counting
fluorescence spectrometer from IBH, U.K. All of the decays were fitted
to a single exponential. The good fit criteria were low χ2 (1.0) and
random distributions of residuals. Cyclic voltammetric studies were
carried out with a BAS electrochemical system utilizing a three-electrode
configuration consisting of glassy carbon (working), platinum wire
(auxiliary), and saturated calomel (reference) electrodes. The experi-
ments were done in dry dichloromethane using 0.1 M tetrabutylammo-
nium perchlorate as the supporting electrolyte. Half-wave potentials
were measured using differential-pulse voltammetry and also calculated
manually by taking the average of the cathodic and anodic peak
potentials. The HRMS spectra were recorded with a Q-Tof micro mass
spectrometer. A single crystal of compound 11 (CCDC 768735) was
in basic and acidic pH media are quite different from each other. In obtained from the slow evaporation of a n-hexane/CHCl3 solution. The
a basic medium, the aldehyde proton Hc appeared at 9.9 ppm, intensity data collection for compound 11 has been carried out on a
which experienced a substantial upfield shift in an acidic medium Nonius MACH3 four-circle diffractometer at 293 K. The structure
and appeared at 5.8 ppm, supporting the existence of compound 9 solution for compound 11 was obtained using direct methods (SHELXS-
in two different states (Scheme 3). These changes are also clearly 97)23 and refined using full-matrix least-squares methods on F2 using
evident in the color of the solutions at different pH under a UV SHELXL- 97.24 For pH studies, the absorption and fluorescence
lamp. At acidic pH, the solution of 9 is bright fluorescent green, titrations were performed in an acetate buffer solution (0.1 M) contain-
which faded at basic pH (Figure S47b in the Supporting In- ing a minimum amount of methanol [1:99 (v/v) CH3OH/buffer] at a
formation). Thus, the pH-controlled fluorescence titration studies probe concentration of 5 μM. A few microliters of 0.1 and 0.01 M
indicate that 3,5-diformylboron dipyrromethenes can be used as solutions of HCl and/or NaOH were used to adjust the pH of the
pH fluorescent sensors. solutions.
Computational Details. The computational studies were per-
’ CONCLUSIONS formed with Gaussian 0319a installed on a Windows operating system.
The structures were energy-optimized using quantum mechanics with
We synthesized stable 3,5-diformylboron dipyrromethenes in DFT19b and B3LYP19c gradient-corrected correlation functional meth-
two steps starting from meso-aryl dipyrromethanes under simple ods in conjugation with a standard 6-31G (p,d) basis set19d and
reaction conditions. The X-ray structural analysis indicated that parameters. For the optimized structures, population analysis studies
the two aldehyde groups are involved in intramolecular hydrogen were done. The redox properties of compounds 9 and 13 and EA and IP
bonding with the fluoride atoms and stabilization of the com- data were also calculated.20,21 Simulations of the addition and removal of
pounds. The formyl groups on the BODIPY framework alter the electrons from BODIPY systems (compounds 9 and 13) were affected
electronic properties of the BODIPY unit siginificantly, which is by simply setting the charges and multiplicities as (
1, 2) and (1, 2).
reflected in various spectroscopic and electrochemical properties. With these charges and multiplicities and the 3D coordinates of neutrally
The electrochemical studies as well as quantum-mechanical optimized BODIPY systems, geometry optimizations were carried out
studies at the DFT level indicated that the BODIPY unit in for the respective anions and cations. From the heats of formation
diformylboron dipyrromethenes is highly electron-deficient and obtained, the total energies (TEs) were calculated by zero-point and
readily undergoes facile reduction. The synthesized 3,5-difor- basis-set corrections. The EA and IP data were calculated using the
mylboron dipyrromethenes were used as fluorescent pH sensors, following formulas:
which is uncommon for aldehyde-containing fluorophores. Pre- EA ¼ TEðneutralÞ
TEðanionÞ
sently, we are using these 3,5-diformylboron dipyrromethenes
to synthesize further eloborated structures such as 3,5-bis- IP ¼ TEðcationÞ
TEðneutralÞ
(dipyrromethane)boron dipyrromethenes (Scheme S1 in the
Supporting Information) for various studies.
1,9-Diformyl-meso-(3,4,5-trimethoxyphenyl) Dipyrro-
’ EXPERIMENTAL SECTION methane. Dimethylformamide (5.1 mmol) was added to a 100 mL
three-neck, round-bottomed flask, cooled to 5
10 °C, and flushed with
General Experimental Details. The 1,9-diformyl dipyrro- nitrogen for 5 min. POCl3 (4.23 mmol) was added dropwise over 15 min
methanes12 5
7 and BODIPY13 13 were synthesized by following the with stirring. Dry dichloroethane (10 mL) was then added, and the
literature procedures. BF3 Et2O and 2,3-dichloro-5,6-dicyano-1,4-ben- mixture was stirred at room temperature for 15 min. The mixture was
zoquinone (DDQ) were used as obtained. All other chemicals used for cooled to 0 °C, meso-(3,4,5-trimethoxyphenyl)dipyrromethane (4; 4.23
the synthesis were reagent-grade unless otherwise specified. Column mmol) in dry dichloroethane (20 mL) was added dropwise over 1 h, and
chromatography was performed on silica (60
120 mesh). The 1H, 13C, the solution turned to deep-purple. The solution was warmed to 50 °C
11
B, and 19F NMR spectra were recorded in CDCl3 using a Varian for 15 min and then allowed to cool to room temperature. A saturated
VXR 400 spectrometer operating at the appropriate frequencies using sodium carbonate solution (50 mL) was added, and the reaction was stir-
tetramethylsilnae [Si(CH3)4] as the internal reference. Absorption and red vigorously at room temperature for 2 h. The mixture was extracted

4398 dx.doi.org/10.1021/ic102499h |Inorg. Chem. 2011, 50, 4392–4400

Inorganic Chemistry ARTICLE

with ethyl acetate (3  100 mL), and the combined organic layers were 151.1, 153.1, 153.6, 184.3. HRMS. Calcd for C20H17BF2N2O5 [(M

dried over Na2SO4, filtered, and evaporated. The crude compound was F)þ]: m/z 395.1215. Found: m/z 395.1197. IR (KBr, νmax): 633.1,
subjected to silica gel column chromatography and eluted with petro- 765.0, 1074.2, 1175.1, 1232.2, 1269.7, 1335.8, 1379.5, 1464.9, 1539.2,
leum ether/ethyl acetate (70:30), which afforded pure 1,9-diformyl- 1570.3, 1675.4, 2922.7.
meso-(3,4,5-trimethoxyphenyl) dipyrromethane (8) as a light-brown
solid in 67% yield (0.8 g). Mp: 168
169 °C. 1H NMR (400 MHz, ’ ASSOCIATED CONTENT
CDCl3, δ in ppm): 3.76 (s, 9H;
OCH3), 5.45 (s, 1H;
CH),
6.07
6.09 (m, 2H; py), 6.63 (s, 2H; Ar), 6.85
6.87 (m, 2H; py),
9.12 (s, 2H;
NH), 10.86 (br s, 2H;
CHO). HRMS. Calcd for
bS Supporting Information. Spectral data of all compounds,
fluorescence data, tables of crystal and absorption data, and X-ray
C20H20N2O5 [(M þ 1)þ]: m/z 369.1450. Found: m/z 369.1436. crystallographic data for compound 11 in CIF format. This material
General Procedure for 3,5-Diformylboron Dipyrro- is available free of charge via the Internet at http://pubs.acs.org.
methenes (9
12). 1,9-Diformyl dipyrromethanes 5
8 (1.7 mmol)
were dissolved in dichloromethane (200 mL) and oxidized with DDQ ’ AUTHOR INFORMATION
(2.04 mmol) at room temperature. The reaction mixture was allowed to
stir at room temperature for 30 min. Triethylamine (68 mmol), followed Corresponding Author
by BF3.Et2O (85 mmol), was added to the reaction mixture successively *E-mail: [email protected].
without any time delay, and stirring was continued at room temperature
for an additional 30 min. The reaction mixture was evaporated, and the
crude product was purified using silica gel column chromatography with ’ ACKNOWLEDGMENT
petroleum ether/ethyl acetate (75:25), which afforded pure 3,5-difor- M.R. acknowledges financial support by the DST and BRNS.
mylboron dipyrromethenes 9
12 as blue-greenish solids. M.R.R. thanks the CSIR for their research fellowship. We thank
3,5-Diformyl-8-tolyl-4-bora-3a,4a-diaza-s-indacene (9). the DST-funded National Single Crystal X-ray Diffraction Facil-
Yield: 80 mg, 14%. Mp: 242
243 °C (dec). 1H NMR (400 MHz, ity for diffraction data. We thank the Department of Chemistry
CDCl3, δ in ppm): 2.52 (s, 3H;
CH3), 7.12 (d, 3J(H,H) = 4.27 Hz, 2H; and Sophisticated Analytical Instrument Facility (SAIF), Indian
py), 7.20 (d, 3J(H,H) = 4.27 Hz, 2H; py), 7.43 (d, 3J(H,H) = 7.94 Hz,
Institute of Technology Bombay, for instrumentation. We also
2H; Ar), 7.53 (d, 3J(H,H) = 7.94 Hz, 2H; Ar), 10.48 (br s, 2H;
CHO).
thank Dr. Evans Coutinho, Bombay College of Pharmacy for
11
B NMR (100 MHz, CDCl3, δ in ppm): 1.26 (t, 1J(B
F), 1B). 19F
providing computational facility and valuable inputs.
NMR (300 MHz, CDCl3, δ in ppm):
130.8 (q, 1J(F
B), 2F). 13C
NMR (100 MHz, CDCl3, δ in ppm): 21.8, 120.2, 129.9, 130.6, 131.4,
132.9, 137.9, 143.8, 151.0, 153.8, 184.4. HRMS. Calcd for C18H13- ’ REFERENCES
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