Polyanils and Polyboranils: Synthesis, Optical Properties, and Aggregation-Induced Emission

Article abstract of DOI:10.1021/acs.joc.6b01756

A first series of polyanils were synthesized by a simple condensation between either isomers of phenylenediamine derivatives or 1,3,5-benzenetriamine and 4-(diethylamino)salicylaldehyde, while a second series resulted from the condensation between 4,6-dih

Full text of DOI:10.1021/acs.joc.6b01756

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Article
Polyanils and polyboranils: Synthesis, Optical
Properties and Aggregation-Induced Emission
Denis Frath, Karima Benelhadj, Maxime Munch, Julien Massue, and Gilles Ulrich
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01756 • Publication Date (Web): 03 Oct 2016
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Polyanils and polyboranils: Synthesis, Optical Properties and Aggregation-
Induced Emission
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Denis Frath, Karima Benelhadj, Maxime Munch, Julien Massue* and Gilles
Ulrich*
Institut de chimie et procédés pour l’énergie, l’environnement et la santé (ICPEES), groupe
Chimie Organique pour les Matériaux, la Biologie et l’Optique (COMBO), UMR CNRS
7515, Ecole Européenne de Chimie, Polymères et Matériaux (ECPM), 25 Rue Becquerel,
67087 Strasbourg Cedex 02, France.
massue@unistra.fr
gulrich@unistra.fr
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Abstract:
A first series of polyanils were synthesized by a simple condensation between either isomers
of
phenylenediamine
derivatives
or
1,3,5ꢀbenzenetriamine
and
4ꢀ
diethylaminosalicylaldehyde, while a second series resulted from the condensation between
4,6ꢀdihydroxyisophthalaldehyde or 2,5ꢀdihydroxyterephthalaldehyde and differently
substituted anilines. All these polyanils showed good chelating abilities towards trivalent
boron fragments such as BF2 or BPh2 to yield the corresponding boranils. The optical
properties of these novel fluorophores have been studied both in solution and in the solidꢀstate
and show emission wavelengths covering the entire visible spectrum and nearꢀinfrared (NIR),
depending on molecular structure, substitution and environment. While faintly fluorescent in
solution in their molecular state, some polyanils show typical aggregationꢀinduced emission
(AIE) behavior upon addition of increasing amount of water in THF solution, leading to a
sizeable enhancement of fluorescence intensity.
Introduction
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Recent literature reports attest from the continuing effort devoted to the development
of innovative organic luminescent fluorophores1 for a wide range of applications in the field
of biotechnologies, from bioimaging contrast agents2 to molecular sensors,3 or embedded in
optoelectronic devices such as photovoltaic cells4 or electroluminescent devices.5
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Among all the synthetic fluorophores studied, very promising features, such as high quantum
yields, fineꢀtuned absorption/emission wavelengths and photostability have been observed for
boron complexes of πꢀconjugated chelates. This family of dyes includes notably the legendary
boron dipyrromethene (BODIPY) family6 but also more recent analogues7 based on N^O,8
N^N9 or N^C10 chelates. In this context, a new family of fluorescent boron complexes, soꢀ
called Boranils, was recently introduced, built around an N^B^O pattern, using anil (anilineꢀ
imine, also called salicylaldimine) ligands.11 The fluorescence emission of anils in solution is
usually very weak due to detrimental intramolecular rotations and/or isomerisation upon
irradiation.7,11,12 Nevertheless, several examples of salicylaldimine13 or salicyladehyde
azines14 have been described to brighten up in the aggregated state due to beneficial
aggregationꢀinduced emission (AIE)15 owing to a sizeable restriction of intramolecular
rotations.16 AIE fluorogens are attractive platforms for bioimaging along with various
biomedical applications.17 Boranils are intrinsically much more fluorescent in the molecular
state than their ligands counterparts due to a beneficial structural rigidification induced by the
presence of the boron fragment.12 Along with promising photophysical properties, boranils
dyes are also interesting candidates for bioconjugation to protein such as Bovine Albumin
Serum (BSA) in biological media.18 Luminescent fluorophores containing several boron
centers are often advantageous over isolated dyes because they seem to contribute to enhance
luminescence intensity, molar absorption coefficient and overall brightness.19 Additionally,
functionalization of multiple boron fragments by sterically hindered substituents can prevent
the formation of detrimental aggregates, leading to enhanced solidꢀstate emission.8c Up to
date, very few examples of polyanils and polyboranils are reported in the literature.20 In this
article, a series of original polyanils and polyboranils are described. They were synthesized in
oneꢀstep synthesis from salicylaldehyde and aniline derivatives and the full optical
characterization of these new fluorophores in solution and in the solidꢀstate was investigated.
Additionally, some polyanils showed AIE behavior upon addition of increasing amounts of
water in THF solution. These highly fluorescent aggregates were characterized by emission
spectroscopy and dynamic lightꢀscattering (DLS).
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Results and discussion
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The synthesis of polyanils 1-5 and polyboranils 6-10 is represented on scheme 1, that
of polyanils 12-13 and polyboranils 14-16 on scheme 2 and that of polyanils 18-19 and
polyboranils 20-21 on scheme 3.
Polyanils 1-5 were synthesized in a oneꢀstep reaction by refluxing commercially available
isomers of phenylenediamine and 4ꢀdiethylaminosalicylaldehyde in absolute ethanol with
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traces amounts of pꢀTsOH (Scheme 1). 1-5 either precipitated pure from the medium or were
purified by column chromatography on silica. Subsequent boron complexation was realized
by the addition of a slight excess of BF3.Et2O on polyanils 1-5 in dry 1,2ꢀdichloroethane
under basic conditions (N,NꢀDiisopropylethylamine (DIEA)). The complexation could be
readily monitored by assessing the disappearance of the distinctive downfield signal
1
corresponding to the Hꢀbonded phenolic proton in H NMR spectroscopy. Polyboranils 6-10
were purified by column chromatography on silica.
Polyanils 12, 13 and 18, 19 were obtained following a similar synthetic route as 1-5, that is by
refluxing 4,6ꢀdihydroxyisophthaldehyde 1121 (Scheme 2) or 2,5ꢀdihydroxyterephthalaldehyde
1722 (Scheme 3) with the corresponding aniline derivative, i.e. 3,4,5ꢀtrimethoxyaniline or 4ꢀ
AminoꢀN,Nꢀdibutylaniline23 in absolute ethanol, followed by purification. The boron
complexation was conducted in the same fashion as for polyboranils 6-10, that is reaction
with an excess of BF3.Et2O in dry 1,2ꢀdichloroethane in the presence of DIEA or with an
excess of BPh3 in toluene in the case of 14 and 20, leading to polyboranils 14-15 and 20-21
after purification by column chromatography on silica gel.
1
All compounds were characterized by H, 13C NMR spectroscopy and HRꢀMS, reflecting
their molecular structure in each case.
Scheme 1. General scheme for the synthesis of polyanils 1-5 and their corresponding
polyboranil complexes 6-10
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Scheme 2. General scheme for the synthesis of polyanils 12 and 13 and their corresponding
polyboranil complexes 14-16.
Scheme 3. General scheme for the synthesis of polyanils 18-19 and their corresponding
polyboranil complexes 20-21.
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1
The aromatic regions of the H NMR spectra of polyanil 19 and its corresponding borate
complex 21 are presented in Figure 1. For polyanil 19, a distinctive downfield peak
corresponding to the Hꢀbonded phenolic protons can be observed (δ = 13.12 ppm). Chelation
to the B(III) fragment can be confirmed, not only by assessing the disappearance of the
phenolic peaks but also by acknowledging a shift of the peak corresponding to the aromatic
protons close to the boron centre. Furthermore, the imine protons, which are observed as a
narrow singlet (δ = 8.57 ppm) in polyanil 19, undergo a pronounced broadening upon
1
complexation. The large singlet which can be observed in the H NMR spectrum of
polyboranil 21, corresponds to a sizeable protonꢀB coupling between the imine proton and the
boron atom, a feature already observed on related derivatives.24
All compounds have been additionally characterized by infraꢀred spectroscopy where they all
display a typical stretching band in the range1610ꢀ1630 cmꢀ1, characteristic of the C=N imine
elongation. Depending on their molecular structures, all dyes investigated display additional
C=C and CꢀH stretching bands in the expected ranges.
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Figure 1. Aromatic regions of the H NMR spectra of polyanil 19 (top) and polyboranil 21
(bottom) in CDCl3 at room temperature.
Photophysical properties of polyanils 1-5, 12-13 and 18-19 are gathered in table 1. Absorption
spectra of polyanils 1-5, 12-13 and 18-19 in THF are presented in Figure 2a while absorption,
emission and excitation spectra of polyanils 3 and 13 are presented in Figure 2b and 2c
respectively.
As a general trend, all polyanil dyes display similar absorption spectra, i.e. a large,
unstructured absorption band located in the UV part of the spectrum between 355 and 436
nm. Additional bands are observed at higher energies and are attributed to the πꢀπ* transitions
of the phenyl rings. Molar absorption coefficients are in the range 21000 to 130100 Mꢀ1.cmꢀ1,
which is consistent for polyaromatic dyes. Polyanil 5 whose structure comprises of three anil
units connected onto a phenyl ring displays the highest molar absorption coefficient in the
series (130100 Mꢀ1.cmꢀ1) while maintaining its maximum absorption wavelength in the UV
(λabs = 393 nm).
Polyanil 19 stands out in the polyanil series since it displays a significant redꢀshifted
maximum absorption wavelength (λabs = 506 nm) compared to other polyanils along with a
high molar absorption coefficient of 75800 Mꢀ1.cmꢀ1. The structured shape of the absorption
band of 19 in THF is characteristic of a merocyanineꢀtype molecular skeleton.
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None of the polyanil dyes studied herein display a sizeable fluorescence in solution in THF
with the notable exception of polyanils 3 and 13 (Figures 2b, 2c). Upon excitation in the
lowestꢀenergy absorption band, 3 and 13 display an intense emission band whose wavelength
peaks at 500 and 606 nm respectively with a quantum yield calculated to be 10 and 3%,
respectively. In both cases, the excitation spectrum matches the absorption one precluding the
presence of emissive aggregates in the excitedꢀstate and ascertaining the molecular species as
the sole emitter. The para conformation of polyanil 3 tends to decrease nonꢀradiative
deactivations in the excitedꢀstate, leading to a sizeable green emission, as compared to its
nonꢀfluorescent isomeric analogues. In the case of 13, the meta conformation seems to be
beneficial for a decrease of the ICT phenomenom, as compared to the full quenched polyanil
19, which displays a para conformation.
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Figure 2. (a) UVꢀVis spectra recorded in THF at room temperature for polyanils 1 (blue), 2
(purple), 3 (red), 4 (dark blue), 5 (dark green), 12 (pink), 13 (light green), 18 (orange) and 19
(yellow) , (b) spectroscopic data for polyanil 3 : absorption (plain blue), excitation (detection
at 515 nm, dashed blue) and emission (λexc = 490 nm, green) and (c) spectroscopic data for
polyanil 13 : absorption (plain blue), excitation (detection at 625 nm, dashed blue) and
emission (λexc = 400 nm, green).
Photophysical data of polyboranils 6-10, 14-16 and 20-21 recorded in solution in various
solvents are collected in table 1 and their absorption and emission spectra recorded in
dichloromethane are displayed in Figures 3 and 4 respectively.
The absorption spectra of all polyboranils compounds, with the notable exception of 21
display similar optical features such a broad, unstructured band, a maximum wavelength
comprised between 370 and 433 nm and molar absorption coefficients ranging from 13100
and 188300 Mꢀ1.cmꢀ1 (figure 3). The absence of structuration of the absorption bands is
presumably related to free rotations occurring in solution. Those features are very similar to
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those observed for their polyanils analogues, such as a very high molar absorption coefficient
(ε = 188300 Mꢀ1.cmꢀ1) for dye 10 which incorporates three anil moieties. Polyboranil 21,
which displays a quadripolar donorꢀacceptorꢀdonor molecular structure, exhibits a maximum
absorption wavelength that is strongly bathochromically shifted as compared to other
polyboranils (λabs = 589 nm in dichloromethane for 21 vs. λabs = 370ꢀ433 nm for 6-10, 14-15
and 20). Moreover, unlike other polyboranil derivatives, the maximum absorption wavelength
of compound 21 seems to be dependent on the dipole moment of the solvent. Indeed, as the
polarity of the solvent increases, the maximum absorption wavelength of 21 undergoes a
significant hypsochromic shift (λabs = 594 nm in toluene to λabs = 473 nm in ethanol). This
reported phenomenon, called inverted solvatochromism25 highlights the presence of a sizeable
dipole moment in the ground state.
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Table 1. Optical data of polyboranils 6-10, 14-16 and 20-21 measured in aerated solution at
room temperature.
ε
λem
ꢁS
λabs
[e]
[g]
dye
[Mꢀ1.cmꢀ1] (nm) (cmꢀ1) Φ F
τ (ns) [f] Solvent kr[g]
knr
(nm) [a]
[b]
[c]
[h]
[h]
[d]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
355
389
416
404
393
364
407
436
506
374
370
417
416
428
434
427
427
427
390
401
423
417
419
62900
82400
76200
57800
130100
29500
57800
21000
75800
71200
62200
110400
112800
68000
90000
72100
66700
88300
51500
109600
148700
145000
188300
THF
THF
1
2
3
4
5
12
13
18
19
6
6
7
7
8
8
8
8
8
[h]
[h]
500
4000
0.10
0.08
THF
THF
THF
THF
12.5 113.0
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
606
8100
0.03
0.15
THF
THF
THF
toluene
CH2Cl2
2.0
64.7
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
457
458
506
510
507
506
504
485
474
460
463
464
1800
1800
3600
3400
3700
3700
3600
4800
3800
1800
2100
2300
0.43
0.01
0.90
0.56
0.78
0.68
0.71
0.10
0.12
0.49
0.01
0.04
0.9
1.2
1.1
1.3
1.2
1.1
1.2
0.3
0.5
0.9
0.1
0.1
CH2Cl2 4.8
CH3CN 0.1
toluene 8.2
CH2Cl2 4.3
6.3
8.3
0.9
3.4
1.8
2.9
2.4
3.0
17.6
5.7
THF
6.5
CH3CN 6.2
acetone 5.9
toluene 3.3
CH2Cl2 2.4
CH2Cl2 5.4
CH3CN 1.0
acetone 4.0
9
9
10
10
10
99.0
96.0
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418
381
473
484
458
462
433
433
594
589
505
473
31600
33900
29200
31200
39400
44000
42700
42200
13100
17300
49800
51000
48200
55200
558
559
7700
8400
0.09
0.06
0.5
0.5
toluene 1.8
CH2Cl2 1.2
toluene 2.0
18.2
18.8
14
14
15
15
16
16
16
16
20
20
21
21
21
21
3
4
5
6
7
8
9
556
[h]
5900
[h]
0.04
[h]
0.2
[h]
48.0
[h]
[h]
CH2Cl2
571
609
635
620
[h]
3600
4900
6100
5500
[h]
0.35
0.21
0.02
0.02
[h]
1.4
1.0
1.0
1.2
[h]
toluene 2.5
CH2Cl2 2.1
acetone 0.2
4.64
7.9
9.8
8.2
[h]
10
11
12
13
14
15
16
17
18
19
20
21
22
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EtOH
toluene
CH2Cl2
0.2
[h]
[h]
[h]
[h]
[h]
[h]
[h]
665
[h]
1700
[h]
0.31
[h]
1.6
[h]
toluene 1.9
4.3
[h]
[h]
CH2Cl2
acetone
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
[h]
EtOH
[a] Maximum absorption wavelength [b] Molar absorption coefficient [c] Maximum emission wavelength [d] Stokes’
shift [e] Quantum yield determined in solution by using quinine sulfate as a reference λ exc = 366 nm, Φ = 0.55 in
1N H2SO4, for dyes emitting below 480 nm, Rhodamine 6G as a reference λ exc = 488 nm, Φ = 0.88 in ethanol,
for dyes emitting between 480 and 570 nm or cresyl violet λ exc = 546 nm, Φ = 0.55 in ethanol as a reference for
[f]
[g]
dyes emitting above 570 nm.
equations: kr = ΦF/τ, knr = (1 ΦF)/τ. [c] non fluorescent.
lifetime
kr (108sꢀ1) and knr (108sꢀ1) were calculated using the following
The emission properties of all polyboranils were tested in a range of solvents with increasing
dipole moment in order to investigate their solvatochromic properties in the excitedꢀstate.
Solubility issues impeded their complete study but dichloromethane was found to be suitable
for comparative studies (Figure 4).
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Figure.3. UVꢀVis spectra recorded in dichloromethane at room temperature for polyboranils
6 (blue), 7 (purple), 8 (red), 9 (dark blue), 10 (dark green), 14 (pink), 15 (grey), 16 (light
green), 20 (orange) and 21 (yellow).
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Figure 4. (a) Emission spectra of polyboranils 7 (λexc = 405 nm, purple), 8 (λexc = 415 nm,
red), 9 (λexc = 390 nm, dark blue), 10 (λexc = 413 nm, dark green), 14 (λexc = 365 nm, pink)
and 16 (λexc = 470 nm, light green) in dichloromethane at room temperature, (b) absorption
(dashed) and emission (λexc = 415 nm, plain) of polyboranil 8 in toluene (purple),
dichloromethane (blue), THF (green), acetone (orange) and acetonitrile (red) and (c)
photographs of dicholoromethane solutions of polyboranils taken under ambient light (top)
and under UVꢀbench lamp (λexc = 365 nm) (bottom).
In dichloromethane, excitation in the lowestꢀenergy absorption band lead to the appearance of
an emission band for polyboranils 7-10, 14 and 16 while the fluorescence of polyboranils 6,
15, 20 and 21 appeared to be fully quenched in solution. Depending on substitution, the
maximum emission wavelength spanned from 457 to 609 nm with quantum yields up to 56%
in dichloromethane. Interestingly, polyboranils 7 and 10 displayed similar optical properties
(λem = 457 nm, Φ = 43% for 7 and λem = 460 nm, Φ = 49% for 10 in dichloromethane). In the
case of dye 10, the connection of an additional boranil fragment does not seem to have an
influence on the optical properties of the resulting polychromophoric scaffold. Polyboranil 8
appears to be the brightest in the series with a quantum yield spanning from 56 to 90%. The
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most striking observation concerning dye 8 is that in polar solvent with a high dipole moment
like acetonitrile, the quantum yield remains high (Φ = 68%), as opposed to the general trend
where a significant increase of nonꢀradiative deactivations, detrimental to the quantum yield is
usually observed as the dipole moment of the solvent increases. The emission wavelength of
polyboranils series 6-10 does not appear to be sensitive to the dielectric constant of the
solvent, highlighting a probable cyanineꢀlike conformation in the excitedꢀstate and a
fluorescence emission presumably stemming from a singlet state. In the case of polyboranils 7
and 10, the quantum yield decreases as the dielectric constant of the solvent increases,
indication the probable presence of a lowꢀlying non emissive charge transfer state.
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Polyboranils 14 and 15 display the same 3,4,5ꢀtrimethoxy substitution and structure but differ
by the nature of the boron fragment, i.e. BPh2 for 14 and BF2 for 15. Introduction of a BPh2
fragment does not seem to make a difference in terms of maximum emission wavelength (λem
= 558 nm for 14 vs. λem = 556 nm for 15 in toluene) which is in contrast with the general trend
observed for other N^B^O borate complexes where substitution of a BF2 group for a BPh2 one
induces a sizeable redꢀshift in emission.26,8c The quantum yield is, however higher in the case
of 14 than for 15 (Φ = 9 and 4% respectively in toluene), evidencing a slight role of the
sterically hindered phenyl rings in reducing nonꢀradiative deactivations. Additionally, the
beneficial introduction of BPh2 is observed in dichloromethane where polyboranil 14 is found
to be fluorescent (λem = 559 nm, Φ = 6%), which is not the case of 15. Further optical studies
in other solvents could not be conducted due to the lack of solubility of 14 and 15.
Polyboranils 14 and 20 feature respectively a 2,4ꢀ or a 2,5ꢀdisubstitution with respect to the
position of the anil moieties. While, as described previously, dye 14 is mildly fluorescent in
toluene or dichloromethane, the fluorescence emission of compound 20 in these two solvents
was found to be completely quenched. This clearly shows that either the 2,5ꢀdisubstitution is
not a good scaffold to provide a good conjugation between the boron centers and the methoxy
substituents on the phenyl rings or that this molecular morphology likely leads to the
detrimental formation of intermolecular aggregates. It is to be noted that attempts to prepare
the BF2 analogue of polyboranil 20 failed due to the lack of stability of the crude product
obtained which could not undergo a purification step. Polyboranils 16 and 21 were found to
be highly soluble in most solvents due to the beneficial presence of solubilizing butyl chains.
In toluene, dye 21 displays a maximum emission wavelength which is located in the red part
of the spectrum and features a striking bathochromic shift as compared to the rest of the series
(λem = 665 nm for 21 vs. λem = 457ꢀ558 nm for other polyboranils in toluene). Another
surprising feature is the value of the quantum yield which remains high (Φ = 31%) for an
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emission located in such low energies. Polyboranil 16 which displays the same electronic
substituents but in a meta fashion is blueꢀshifted in absorption and emission in toluene, as
compared to 21 (λabs = 473 nm, λem = 571 nm, Φ = 35%). To investigate the solvatochromic
nature of the emission band, the optical properties of 16 and 21 were studied in solvents of
increasing dipole moment. While the absorption of 16 does not undergo any major change
upon increase of the dipole moment of the solvent, the emission maximum wavelength spans
from 571 to 635 nm depending on solvent with a significant decrease of the fluorescence
quantum yield. Unfortunately, the emission of 21 was found to be completely quenched
outside toluene, probably due to an important internal charge transfer (ICT) character of the
emission.27 To evidence the presence of a sizeable ICT in 21, protonation studies were
conducted in the presence of HClgas and the results in dichloromethane and acetone are shown
in figure 5.
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Figure 5. Absorption (dashed) and emission (λexc = 490 nm, plain) spectra of polyboranil 21
in dichloromethane in the neutral (blue) protonated state (green) at room temperature and
(inset) photographs of polyboranils 21 in the neutral and protonated state in solution in
dichloromethane under ambient light (left) and under UVꢀbench lamp (λexc = 365 nm) (right).
Protonation experiments were conducted by bubbling HClgas in a dichloromethane or acetone
solution of 21. First, upon protonation of the lone electron pair of the nitrogen atoms,
maximum absorption wavelengths displayed a strong hypsochromic shift along with a
hypochromic value of their molar absorption coefficient (λabs = 589 nm, ε = 51000 Mꢀ1.cmꢀ1
vs. λabs = 495 nm, ε = 9400 Mꢀ1.cmꢀ1 for 21 in neutral and protonated dichloromethane
respectively and λabs = 505 nm, ε = 48200 Mꢀ1.cmꢀ1 vs. λabs = 466 nm, ε = 6800 Mꢀ1.cmꢀ1 for
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21 in neutral and protonated acetone respectively). This absorption change phenomenom has
been previously observed for related borate complexes based on isoquinoline framework.28
Although completely quenched in dichloromethane and acetone in the neutral state,
polyboranil 21 was found to sizably brighten up upon protonation. Indeed, excitation in the
lowestꢀenergy absorption band lead to the appearance of an intense emission band located in
the orange, in the case of the two solvents (λem = 640 nm, Φ = 24% in dichloromethane and
λem = 620 nm, Φ = 5% in acetone). This is a clear indication that the emission in polyboranil
21 stems from an excitedꢀstate with a strong ICT character. In the neutral state, a significant
electronic delocalization occurs in the ground and the excitedꢀstate between the aromatic
amine (donor) and the BF2 fragment; 21 acting as a typical pushꢀpull fluorophore.29 This leads
to both a solvatochromic behavior in absorption. Upon protonation, the delocalization is no
longer possible making the ICT much weaker, leading to a hypsochromic shift in absorption
and the appearance of a significant emission in dichloromethane and acetone. Protonation
studies were also performed on polyboranil 16 and the trends observed in 21 were similarly
found (λabs = 484 nm, λem = 608 nm, Φ = 21% vs. λabs = 380 nm, λem = 442 nm, Φ = 8% for
16 in neutral and protonated dichloromethane respectively).
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Table 2. Optical data of polyanils 2-5 and polyboranils 6-10, 14 and 20-21 measured in the
solidꢀstate as KBr pellets
λexc
ꢁS
λem
x;y
(CIE 1931)
[
a]
Dye
Φ f
(cmꢀ1)
(nm)
(nm)
476
512
484
498
556
465
489
529
487
474
443
576
550
692
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554
514
591
644
601
525
560
588
534
541
642
720
789
2760 0.04 0.377 ;0.420
1480 0.11 0.506 ;0.474
1200 0.06 0.438 ;0.388
3200 0.06 0.438 ;0.384
2500 0.05 0.680; 0.325
4900 0.05 0.444 ;0.395
1400 0.10 0.389 ;0.473
1050 0.22 0.491 ;0.436
3500 0.05 0.449 ;0.381
2400 0.07 0.434 ;0.405
4100 0.18 0.222 ;0.455
1800 0.10 0.691; 0.309
4300 0.30 0.713 ;0.288
2
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5
13
6
7
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9
10
14
16
20
21
[b]
[b]
1800
[a]
[b]
Absolute quantum yield, calculated with an integrating sphere. the emission of polyboranil 21 is located in
the near infraꢀred (NIR) and the quantum yield cannot be accurately calculated with our current
spectrophotometer.
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The emission properties of all polyanils and polyboranils were studied in the solidꢀstate as
embedded in KBr pellets (concentration around 10ꢀ6M). The optical data are presented in table
2 while the emission spectra of polyanils 2-5 and 13 and polyboranils 6-10, 14, 16 and 20-21
are displayed in figures 6a and 6b respectively.
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Figure 6. Emission (λexc = 400 nm) spectra recorded in the solidꢀstate, in KBr pellets of (a)
polyanils 2 (purple), 3 (red), 4 (dark blue), 5 (dark green) and 13 (light green) and (b)
polyboranils 6 (blue), 7 (purple), 8 (red), 9 (dark blue), 10 (green), 14 (grey), 16 (light green),
20 (orange) and 21 (yellow).
As a general observation, the emission profiles for all studied compounds follow the same
trends as those observed in the solution state, i.e. broad, unstructured emission bands covering
most of the visible spectrum depending on substitution, except for para substituted derivatives
3 and 8 comprising of a cyanineꢀlike structure, which display a relatively structured emission
band.
First, it is to be noted that polyanils 2,4 and 5 are slightly emissive in the solidꢀstate whereas
they were fully quenched in solution in THF (λem = 514ꢀ591 nm) (figure 6a). The quantum
yields, calculated with a spectrofluorimeter fitted with an integration sphere are in the range
4ꢀ6%. Polyanil 3 exhibits a structured emission band with a maximum wavelength at 554 nm
and a quantum yield of 11%, which corresponds to a significant redꢀshift as compared to its
emission profile in solution (λem = 500 nm, Φ = 10% in THF). Embedment in a confined
matrix seems to be beneficial for the sizeable decrease of nonꢀradiative deactivations due to
the restriction of molecular rotations and torsions. Similar conclusions can be drawn for
polyboranils 6 and 20 whose fluorescence was switched off in solution but fully on in the
solidꢀstate (λem = 601 nm, Φ = 5% and λem = 720 nm, Φ = 30% for 6 and 20 respectively).
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This observation is especially striking for polyboranil 20 which displays, in the solidꢀstate an
emission band located in the farꢀred region with a strong quantum yield of 30%; a value rarely
calculated for such small energy radiations. This is particularly interesting, owing to the broad
number of applications arising from bright solidꢀstate emitters.30
9
Polyboranils 7-10 and 21 which were already fluorescent in solution all undergo a
bathochromic shift in solidꢀstate emission more or less pronounced depending on substitution.
Polyboranils dyes 7-10 display an emission wavelength in the visible region, in the range 525ꢀ
588 nm while 21 exhibits an emission wavelength in the near infraꢀred (NIR) region at 789
nm. Polyboranil 14 is the only dye in the series to exhibit a slight blueꢀshift upon insertion in
a solid matrix (λem = 541 nm, Φ = 18%).
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Recent publications report the AIE behavior of related functionalized anil derivatives in
mixtures of solvent15 which prompted us to examine the aggregation ability of the various
polyanils dyes developed in our study and evaluate their potential use as multicolor
fluorogens.
Figure 7. (left) Fluorescence emission spectra in THF with different water fraction at pH 7.4
buffered by PBS 0.1M and (right) Fluorescence emission peak intensity at 528 nm as a
function of water fraction for (a) polyanil 2 and (b) polyanil 5. Polyanils were excited at 400
nm. Photographs were taken under UV light at 365 nm.
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First, the AIE behavior of the polyanil derivatives 1, 2, 4 and 5 were tested by adding
increasing amounts of water (water fraction, named fw from 0% to 98%), buffered by PBS
(0.1 M) at pH 7.4. These polyanils dyes were not fluorescent in THF solution. In the
aggregated state, excitation at 400 nm lead to the appearance of a sizeable emission of light at
a maximum wavelength of 528 nm in the case of 2 and 5 at a concentration of 50 µM.
Polyanils 1 and 4 did not display detectable AIE behavior. The emission spectra of 2 and 5 are
displayed in figure 7a and 7b respectively.
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As shown of figures 7a and 7b, dyes 2 and 5 were not fluorescent in pure THF solution and
the emission intensity, monitored at 528 nm did not show any increase before fw reached 60%
and 40% for 2 and 5 respectively. At this point, the intensity at 528 nm started to rise steeply
to reach a maximum value for fw 98%. This intensity enhancement represents a 25ꢀfold and
46ꢀfold increase for polyanils 2 and 5 respectively from THF solution to the 98% aqueous
mixture.
Then, similar AIE experiments were carried out on polyanil 3 which already displays
fluorescence in THF solution (λem = 500 nm, Φ = 10%). The emission spectra recorded upon
increase of fw along with the evolution of the intensity of the emission band at 552nm are
collected in figure 8.
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Figure 8. (a) Fluorescence emission spectra in THF with water fraction from 0 to 60% at pH
7.4 buffered by PBS 0.1M, (b) Fluorescence emission spectra in THF with water fraction
from 60 to 100% at pH 7.4 buffered by PBS 0.1M, (c) Photographs of solutions of 3 in
THF/PBS with water fraction from 0 to 100% (left to right) taken under UV light at 365 nm,
and (d) Fluorescence emission peak intensity at 552 nm as a function of water fraction for
polyanil 3. Excitation was 400 nm.
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Addition of increasing amounts of water leads to the appearance of an additional emission
band at a longer wavelength compared to that observed in pure THF (λem = 552 nm vs. λem
=
500 nm in THF). The intensity at 552 nm first started to rise softly up to fw 40%, leading to a
dual emission at 500 and 552 nm, corresponding to the presence of 3 in the molecular and the
aggregated state respectively. Upon further increase of fw, a steep enhancement up to fw 60%
can be evidenced in the fw/Intensity at 552 nm plot. From that point on, the intensity was
observed to decrease rapidly down to fw 80% before reaching a plateau between fw 80% and
98%. This AIE behavior is in strong contrast to typical AIE behavior observed for 2, 5 or
related probes13 where the fluorescence intensity gradually increases along with fw. The
intensity enhancement represented a 42ꢀfold increase at 60% aqueous mixture before
dropping to an 11ꢀfold increase at 80%.
To shed more light on the nature of these aggregates, dynamic lightꢀscattering (DLS)
experiments were conducted for polyanils 2 and 5 in 98% aqueous solution and for polyanil 3
in 60% and 98% aqueous solutions. For each dye, DLS measurements were repeated ten
times, each time comprising of ten scans and average results are reported in figures S3ꢀS6.
For polyanils 2 and 5, aggregates with an average size of 150 nm and 75 nm respectively were
measured in 98% aqueous solutions. It is to be noted that these aggregates are stable overtime
in solution and no dissociation could be observed after 48 hours. For polyanil 3, in a 60/40
THF/water mixture, DLS experiments revealed a particle size of the aggregates in the range
100ꢀ300 nm, consisted with previously reported literature probes.13c Additional particles are
observed in the nanometer range, probably corresponding to the molecular species still
present in solution, as evidenced by the presence of the emission band at 500 nm at fw 60%.
Upon increase of fw at 98%, the size distribution evolved largely towards the presence of both
larger aggregates in the micrometer range and smaller particles evidencing a sizeable
dissociation of the aggregates. This hypothesis is also supported by the steep decrease of the
intensity at 552 nm upon the increase of fw.
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In conclusion, two series of polyanils were constructed in oneꢀstep synthesis from
salicyladehydes and anilines, followed by a boron complexation to form the polyboranils.
Polyboranil dyes display sizeable emission properties in solution and in the solidꢀstate,
covering the entire visible spectrum and even reaching NIR in the condensed matter.
Polyanils are faintly fluorescent in solution but display interesting AIE behaviors in
THF/water solutions. In the aggregated state, up to a 46ꢀfold enhancement of the intensity was
observed. Structural modifications such as extension of conjugation is currently under
investigation to target redꢀshifted aggregates and evaluate their role as biological probes.
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EXPERIMENTAL SECTION
All reactions were performed under a dry atmosphere of argon using standard Schlenk
techniques. All chemicals were received from commercial sources and used without further
purification. Dichloromethane and 1,2ꢀdichloroethane were distilled over P2O5 under an argon
atmosphere. Thin layer chromatography (TLC) was performed on silica gel coated with
fluorescent indicator. Chromatographic purifications were conducted using 40ꢀ63 ꢂm silica
gel. All mixtures of solvents are given in v/v ratio.
1H NMR (400.1 MHz) and 13C NMR (100.5 MHz) spectra were recorded on a 400 MHz
1
13
spectrometer, H NMR (300.1 MHz) and C NMR (75.5 MHz) or a 300 MHz spectrometer
with perdeuterated solvents with residual protonated solvent signals as internal references.
High resolution mass spectra (HRMS) data were recorded on a microTOF spectrometer
equipped with orthogonal electrospray interface (ESI).
Absorption spectra were recorded using a dualꢀbeam grating absorption spectrometer with a 1
cm quartz cell. The steadyꢀstate fluorescence emission and excitation spectra were obtained
by using a fluorimeter. Solvents for spectroscopy were spectroscopic grade and were used as
received. All fluorescence spectra were corrected.
The fluorescence quantum yield (Φexp) was calculated from eq (1):
I denotes the integral of the corrected emission spectrum, f is the absorption factor at the
excitation wavelength, and η is the refractive index of the medium. Quantum yield is
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determined in solution by using quinine sulfate as a reference λ exc = 366 nm, Φ = 0.55 in 1N
H2SO4, for dyes emitting below 480 nm, Rhodamine 6G as a reference λ exc = 488 nm, Φ =
0.88 in ethanol, for dyes emitting between 480 and 570 nm or cresyl violet λ exc = 546 nm, Φ
= 0.55 in ethanol as a reference for dyes emitting above 570 nm. The reference quantum
yields were obtained using reported procedures.31
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Solidꢀstate absolute quantum yield were determined using an integrating sphere.32
Luminescence lifetimes were measured on a spectrofluorimeter equipped with a R928
photomultiplier and a pulsed diode connected to a delay generator. No filter was used for the
excitation. Emission wavelengths were selected by a monochromator. Lifetimes were
deconvoluted with FSꢀ900 software using a lightꢀscattering solution for instrument response.
The excitation source was a laser diode (λexc = 320 nm).
IR spectra of were recorded on neat products (powder samples) using ATR diamond plate.
4,6ꢀdihydroxyisophthaldehyde 11,20 2,5ꢀdihydroxyterephthalaldehyde 17,21 4ꢀAminoꢀN,Nꢀ
dibutylaniline,22 polyanil 1,33 polyanil 2,34 polyanil 311a and polyboranil 811a were synthesized
according to reported procedures.
General procedure I for the synthesis of polyanils 1-5, 12-13 and 18-19 To a solution of
0.2 mmol the relevant diꢀ or trianiline in 20 mL of dry ethanol was added the corresponding
salicylaldehyde (0.4 mmol, 2 eqts) as a powder. pTsOH (one crystal) was then added to the
mixture and the resulting solution was refluxed overnight. After cooling down, either a
precipitate appears which was collected, further washed with ethanol and pentane and dried
under vacuum or purification was performed by column chromatography on silica, using
CH2Cl2 as eluent to yield the desired polyanil 1-5, 12-13 and 18-19 as yellow to red powders
(28 to 87% yield).
Polyanil 4.35 The general procedure I was followed leading to 4 as a yellow crystalline
powder 44% (45 mg). mp 290°C (decomp.); 1H NMR (300 MHz, CDCl3) δ (ppm): 13.85 (1H,
3
3
s), 8.49 (1H, s), 8.17 (2H, d, J = 8.3 Hz), 7.52 (2H, t, J = 7.3 Hz), 7.22 (4H, m), 6.30 (4H,
3
3
m), 3.44 (8H, q, J = 7.3 Hz), 1.24 (12H, t, J = 7.3 Hz). ESIꢀHRMS: calcd for
C32H37N4O2 509.2911 (M+H), found 509.2941 (M+H). IR (ν, cmꢀ1):1620.8, 1581.5, 1515.2,
1447.9, 1425.3, 1391.4, 1374.1, 1344.3, 1305.2, 1235.8, 1219.6, 1191.1, 1075.7, 934.5, 821.3,
779.8.
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Polyanil 5. The general procedure I was followed leading to 5 as a yellow crystalline
4
5
1
powder in 59% yield (77 mg). mp 240°C; H NMR (300 MHz, Acetoneꢀd6) δ (ppm): 13.47
(3H, s), 8.79 (3H, s), 7.34 (3H, d, 3J = 9.1 Hz), 7.12 (3H, s), 6.37 (3H, dd, 3J = 9.1 Hz, 4J = 2.4
Hz), 6.15 (3H, d, 4J = 2.4 Hz), 3.48 (12H, q, J = 7.3 Hz), 1.20 (18H, t, J = 7.3 Hz); 13C NMR
(75 MHz, CDCl3) δ (ppm): 164.6, 161.0, 152.2, 150.8, 134.2, 110.5, 109.3, 104.1, 98.0, 44.8,
12.9. ESIꢀHRMS: calcd for C39H49N6O3 649.3861 (M+H), found 649.3884 (M+H). IR (ν, cmꢀ
1): 1625.7, 1564.2, 1513.6, 1416.9, 1340.8, 1239.1, 1124.8, 1076.8, 785.6.
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Polyanil 12. The general procedure I was followed leading to 12 as a yellow crystalline
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powder in 47% yield (47 mg). mp 268ꢀ270°C H NMR (400 MHz, CDCl3) δ (ppm) = 14.12
(s, 2H), 8.79 (br s, 2H), 7.45 (s, 1H), 6.57 (s, 1H), 6.51 (s, 4H), 3.91 (s, 12H), 3.87 (s, 6H).
13C NMR (75 MHz, CDCl3) δ (ppm) = 166.5, 160.2, 154.0, 144.0, 137.8, 113.2, 104.6, 98.6,
92.9, 61.2, 56.4. ESIꢀHRMS: calcd for C26H29N2O8 497.1918 (M+H), found 497.1950
(M+H). IR (ν, cmꢀ1): 1624.5, 1578.9, 1499.8, 1459.7, 1415.7, 1362.1, 1228.1, 1178.3, 1127.6,
992.6, 837.5, 815.2, 794.6.
Polyanil 13 The general procedure I was followed leading to 13 as a red amorphous
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powder in 75% yield (76 mg). H NMR (400 MHz, CDCl3) δ (ppm) = 14.82 (s, 2H), 8.50 (s,
3
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2H), 7.30 (s, 1H), 7.22 (d, 4H, J = 9.2 Hz), 6.66 (d, 4H, J = 8.8 Hz), 6.50 (s, 1H), 3.30 (t,
3
8H, J = 7.2 Hz), 1.58ꢀ1.63 (m, 8H), 1.33ꢀ1.42 (m, 8H), 0.97 (t, 12H, 3J = 7.6 Hz). 13C NMR
(75 MHz, CDCl3) δ (ppm) = 166.2, 155.5, 147.4, 135.7, 135.2, 122.0, 113.3, 112.0, 104.4,
51.0, 29.5, 20.4, 14.0. ESIꢀHRMS: calcd for C36H51N4O2, 571.4007 (M+H), found 571.3955
(M+H). IR (ν, cmꢀ1): 1621.7, 1604.2, 1512.5, 1397.0, 1360.0, 1283.9, 1220.8, 1179.2, 1153.2,
1109.6, 926.4, 877.4, 842.9, 809.0, 798.1, 732.7, 528.3.
Polyanil 18. The general procedure I was followed leading to 18 as a yellow crystalline
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powder in 87% yield (86 mg). mp 252°C H NMR (400 MHz, CDCl3) δ (ppm) = 12.59 (br s,
2H), 8.63 (s, 2H), 7.14 (s, 2H), 6.59 (s, 4H), 3.93 (s, 12H), 3.89 (s, 6H). 13C NMR (100 MHz,
CDCl3) δ (ppm) = 161.0, 154.0, 153.1, 144.1, 137.9, 122.5, 119.3, 98.8, 61.2, 56.4. ESIꢀ
HRMS: calcd for C26H29N2O8, 497.1918 (M+H), found 497.1940 (M+H). IR (ν, cmꢀ1):
1586.0, 1502.3, 1467.3, 1327.1, 1232.3, 1163.4, 1131.5, 1002.8, 991.0, 824.6, 783.2, 642.8,
625.1.
Polyanil 19. The general procedure I was followed leading to 19 as a red crystalline
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powder in 28% yield (32 mg). mp 127ꢀ128°C H NMR (300 MHz, CDCl3) δ (ppm) = 13.13
(s, 2H), 8.57 (s, 2H), 7.28 (d, 4H, 3J = 9.0 Hz), 6.96 (s, 2H), 6.66 (d, 4H, 3J = 9.0 Hz), 3.33ꢀ
3.28 (t, 8H, 3J = 7.5 Hz), 1.65ꢀ1.57 (m, 8H), 1.44ꢀ1.31 (m, 8H), 0.97 (t, 12H, 3J = 7.3 Hz). 13C
NMR (75.5 MHz, CDCl3) δ (ppm) = 155.6, 152.9, 148.1, 135.9, 122.8, 122.4, 118.1, 112.1,
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51.1, 29.6, 20.5, 14.2. ESIꢀHRMS: calcd for C36H51N4O2, 571.4007 (M+H), found 571.3981
(M+H). IR (ν, cmꢀ1): 1609.1, 1572.9, 1501.4, 1366.5, 1349.0, 1333.5, 1314.7, 1211.4, 1172.9,
1155.4, 925.3, 879.2, 854.0, 812.5, 787.0, 523.6.
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General procedure II for the synthesis of polyboranils 6-10, 15, 16 and 21 To a stirred
solution of 0.2 mmol of the relevant polyanil 1-5, 12-13 or 19 in 20 mL of distilled 1,2ꢀ
dichloroethane at 85°C was added BF3.OEt2 (0.5 mmol, 2.5 eqts.). A color change
immediately occurs or a precipitate appears revealing the formation of an inꢀsitu intermediary.
N,NꢀDiisopropylethylamine (DIEA) (0.5 mmol, 2.5 eqts.) was then added dropwise to the
medium and the course of the reaction was monitored by TLC analysis. After cooling down,
the reaction mixture was washed with a saturated solution of NaHCO3 and extracted with
dichloromethane three times. Organic layers were dried over MgSO4 and the solvents
evaporated in vacuo. Polyboranils 6-10, 15ꢀ16 and 21 were purified by silica or alumina gel
chromatography (using CH2Cl2/Pet.ether 1:1 and CH2Cl2 as eluent respectively) and obtained
pure as yellow to purple powders (37 to 96% yield).
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Polyboranil 6. The general procedure II was followed leading to 6 as a yellow crystalline
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powder in 74% yield (82 mg). mp 253°C H NMR (300 MHz, CDCl3) δ (ppm): 8.09 (2H, br
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3
4
s), 7.65 (2H, m), 7.40 (2H, m), 7.13 (2H, d, J = 9.1 Hz), 6.24 (2H, dd, J = 9.1 Hz, J = 2.2
4
13
Hz), 6.12 (2H, d, J = 2.2 Hz), 3.38 (8H, q, J = 6.9 Hz), 1.18 (12H, t, J = 6.9 Hz); C NMR
(75.5 MHz, CDCl3) δ (ppm): 163.5, 162.0, 156.7, 138.3, 135.0, 128.7, 128.4, 106.8, 98.1,
45.3, 12.9). ESIꢀHRMS: calcd for C28H33B2F4N4O2, 555.2730 (M+H), found 555.2728
(M+H). IR (ν, cmꢀ1): 1628.1, 1606.6, 1583.0, 1445.1, 1350.0, 1223.3, 1190.0, 1072.0, 1039.7,
973.4, 821.4, 791.4, 526.9.
Polyboranil 7. The general procedure II was followed leading to 7 as a yellow crystalline
1
powder in 94% yield (104 mg). mp 282ꢀ285°C H NMR (300 MHz, CDCl3) δ (ppm): 8.10
(2H, s), 7.53 (4H, m), 7.28 (2H, m), 6.39 (2H, dd, 3J = 9.2 Hz, 4J = 2.4 Hz), 6.24 (2H, d, 4J =
2.4 Hz), 3.46 (8H, q, J = 7.3 Hz), 1.25 (12H, t, J = 7.3 Hz); 13C NMR (75.5 MHz, DMSOꢀd6)
δ (ppm): 161.0, 159.9, 156.1, 143.6, 135.0, 121.8, 106.9, 96.7, 44.5, 12.5. ESIꢀHRMS: calcd
for C28H33B2F4N4O2, 555.2730 (M+H), found 555.2704 (M+H). IR (ν, cmꢀ1): 1624.6, 1577.6,
1505.5, 1473.5, 1456.7, 1372.5, 1344.8, 1261.4, 1189.4, 1177.6, 1144.5, 1077.5, 1031.5,
968.0, 792.5, 783.6, 643.6, 531.8.
Polyboranil 9. The general procedure II was followed leading to 9 as a yellow crystalline
powder in 84% yield (102 mg).mp 240°C 1H NMR (300MHz, CDCl3) δ (ppm): 7.93 (4H, m),
3
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7.58 (4H, m), 7.23 (2H, d, J = 9.3 Hz), 6.39 (2H, d, J = 9.3. Hz), 6.32 (2H, s), 3.48 (8H, q,
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3J = 7,3 Hz), 1.27 (12H, t, J = 7,3 Hz); C NMR (75.5MHz, CDCl3) δ (ppm): 162.4, 156.7,
140.0, 134.3, 130.8, 126.6, 124.4, 123.8, 107.0, 106.3, 98.5, 45.5, 12.9. ESIꢀHRMS: calcd for
C32H35B2F4N4O2, 605.2888 (M+H), found 605.2856 (M+H). IR (ν, cmꢀ1): 1620.1, 1591.1,
1502.4, 1447.0, 1402.4, 1345.0, 1233.4, 1142.0, 1071.6, 1035.7, 965.5, 784.1, 525.7.
Polyboranil 10. The general procedure II was followed leading to 10 as a yellow
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amorphous powder in 63% yield (105 mg). H NMR (300 MHz, CDCl3) δ (ppm): 8.18 (3H,
br s), 7.66 (3H, s), 7.37 (3H, d,3J = 8.8 Hz), 6.41 (3H, d, 3J = 8.8 Hz), 6.23 (3H, s), 3.47 (12H,
q, J = 6.9 Hz), 1.26 (18H, t, J = 6.9 Hz); 13C NMR (75.5 MHz, CDCl3) δ (ppm): 158.3,
157.8, 134.7, 116.5, 107.2, 98.0, 45.3, 12.7. ESIꢀHRMS: calcd for C39H45B3F6KN6O3,
831.3387 (M+K), found 831.3414 (M+K). IR (ν, cmꢀ1): 1622.3, 1575.2, 1504.6, 1455.8,
1417.0, 1343.7, 1260.9, 1175.6, 1142.1, 1071.7, 1031.8, 968.3, 889.2, 860.2, 820.9, 787.9,
715.7, 650.1, 526.2.
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Polyboranil 15. The general procedure II was followed leading to 15 as a red crystalline
powder in 37% yield (44 mg). mp 292ꢀ293°C 1H NMR (300 MHz, CDCl3) δ (ppm) = 8.38 (br
s, 2H), 7.81 (s, 1H), 6.76 (s, 1H), 6.74 (s, 4H), 3.90 (s, 12H), 3.89 (s, 6H). 13C NMR (75
MHz, CDCl3) δ (ppm) = 166.9, 161.1, 154.0, 140.0, 139.4, 137.9, 112.0, 107.7, 101.3, 92.9,
61.2, 56.6. ESIꢀHRMS: calcd for C26H26B2F4KN2O8, 631.1452 (M+K), found 631.1457
(M+K). IR (ν, cmꢀ1): 1635.8, 1597.4, 1579.1, 1464.8, 1410.9, 1337.8, 1224.9, 1172.9, 1122.8,
1033.2, 1013.1, 994.1, 931.0, 852.6, 834.6, 797.9, 648.0, 623.6.
Polyboranil 16. The general procedure II was followed leading to 16 as a purple
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amorphous powder in 79% yield (105 mg). H NMR (400 MHz, CDCl3) δ (ppm) = 8.19 (s,
3
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2H), 7.61 (s, 1H), 7.33 (d, 4H, J = 8.8 Hz), 6.64 (s, 1H), 6.59 (d, 4H, J = 8.8 Hz), 3.27 (t,
8H, J = 7.2 Hz), 1.51ꢀ1.59 (m, 8H), 1.30ꢀ1.40 (m, 8H), 0.96 (t, 12H, 3J = 7.6 Hz). 13C NMR
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(75 MHz, CDCl3) δ (ppm) = 165.3, 156.3, 148.8, 137.6, 129.6, 123.9, 112.1, 111.6, 106.9,
50.9, 29.3, 20.3, 14.0. ESIꢀHRMS: calcd for C36H49B2F4N4O2, 667.3984 (M+H), found
667.399. IR (ν, cmꢀ1): 1628.6, 1604.7, 1514.5, 1400.2, 1364.8, 1211.3, 1180.1, 1029.4, 954.6,
926.2, 893.1, 854.3, 807.6, 720.0, 532.8.
Polyboranil 21. The general procedure II was followed, leading to 21 as a purple
amorphous powder in 96% yield (128 mg). 1H NMR (300 MHz, CDCl3) δ (ppm) = 8.36 (br s,
3
3
2H), 7.55 (d, 4H, J = 8.7 Hz), 7.06 (s, 2H), 6.69 (d, 4H, J = 8.7 Hz), 3.36ꢀ3.31 (m, 8H),
1.63ꢀ1.58 (m, 8H), 1.42ꢀ1.34 (m, 8H), 0.98 (t, 12H, 3J = 7.3 Hz). 13C NMR (75 MHz, CDCl3)
δ (ppm) = 156.3, 150.2, 149.4, 129.9, 124.6, 122.8, 119.4, 111.8, 51.0, 29.3, 20.3, 14.0. ESIꢀ
HRMS: calcd for C37H48B2F4N4O2, 667.3984 (M+H), found 667.3970 (M+H). IR (ν, cmꢀ1):
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1608.8, 1589.2, 1518.4, 1483.2, 1456.8, 1404.6, 1364.0, 1287.2, 1183.5, 1108.9, 1052.2,
925.7, 877.8, 813.3, 546.8.
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General procedure III for the synthesis of polyboranils 14 and 20 To a stirred solution
of 0.2 mmol of the relevant polyanil 12 or 18 in 20 mL of distilled toluene was added BPh3
(0.3 mmol, 1.5 eqts.) as a powder. The resulting mixture was stirred at 90°C and the course of
the reaction was monitored by TLC analysis. When the reaction was complete, it was allowed
to cool down. The solvent was removed in vacuo and the residue was purified by silica gel
chromatography using CH2Cl2 as eluent, to yield polyboranils 14 or 20 as yellow powders (33
to 89% yield).
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Polyboranil 14. The general procedure III was followed, leading to 14 as a yellow
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amorphous powder in 33% yield (55 mg). H NMR (300 MHz, CDCl3) δ (ppm) = 8.16 (br s,
2H), 7.43ꢀ7.37 (m, 8H), 7.37 (s, 1H),7.26ꢀ7.19 (m, 12H), 6.62 (s, 1H), 6.15 (s, 4H), 3.80 (s,
13
6H), 3.54 (s, 12H). C NMR (75 MHz, CDCl3) δ (ppm) = 169.9, 160.4, 153.0, 141.1, 140.1,
138.1, 134.8, 133.5, 131.2, 128.1, 127.3, 126.9, 112.8, 107.7, 102.9, 61.1, 56.3. ESIꢀHRMS:
calcd for C50H47B2N2O8, 825.3529 (M+H), found 825.3514 (M+H). IR (ν, cmꢀ1): 1635.6,
1629.0, 1578.2, 1503.1, 1465.6, 1333.1, 1240.4, 1125.6, 1183.0, 1048.3, 1006.4.
Polyboranil 20. The general procedure III was followed, leading to 20 as a yellow
crystalline powder in 89% yield (151 mg). mp 275°C (decomp.). 1H NMR (300 MHz, CDCl3)
δ (ppm) = 8.35 (s, 2H), 7.43ꢀ7.40 (m, 8H), 7.24ꢀ7.19 (m, 12H), 7.05 (s, 2H), 6.24 (s, 4H),
3.79 (s, 6H), 3.57 (s, 12H). 13C NMR (75 MHz, CDCl3) δ (ppm) = 162.3, 153.5, 153.0, 141.0,
138.6, 134.8, 133.7, 131.22, 129.8, 128.1, 127.3, 126.8, 125.7, 121.4, 121.0, 115.4, 102.7,
99.1, 61.1, 56.3. ESIꢀHRMS: calcd for C50H46B2N2NaO8, 847.3332 (M+Na), found 847.3322
(M+Na). IR (ν, cmꢀ1): 1594.2, 1577.4, 1433.5, 1252.4, 1232.8, 1162.1, 1131.9, 1003.0, 988.3,
965.0, 840.8, 744.4, 730.7, 704.3, 688.2, 632.2, 619.2, 523.0.
ACKNOWLEDGEMENTS
J.M. and G.U. thank the Centre National de la Recherche Scientifique (CNRS) for funding,
D.F. and K.B. thank the Ministère de l’Education Nationale, de la Recherche et de
l’Enseignement Supérieur for a Ph.D. grant and M.M. thanks the Région Alsace and Amoneta
Diagnostics for a Ph.D. grant.
Supporting Information
The supporting information is available free of charge on the ACS Publications website.
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13C NMR spectrum was not obtained due inherent insolubility of 4 in CDCl3 or
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