Tunable photophysical properties of thiophene based chromophores: A conjoined experimental and theoretical investigation

Article abstract of DOI:10.1039/c9nj00575g

In this paper we report the synthesis and photophysical properties of six novel thiophene derivatives (ThD) with D-π-A structure. The subject of this work is three nitrophenyls (1) BT-Th-NO₂ and three benzonitriles (2) BT-Th-CN, substituted at

Full text of DOI:10.1039/c9nj00575g

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Cheret, A. Grabarz, P. Haczyc, P. Fita, A. El-Ghayoury, L. Sznitko, J. Mysliwiec and B. Sahraoui, New J.
Chem., 2019, DOI: 10.1039/C9NJ00575G.
Volume 40 Number
1
January 2016 Pages 1–846
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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

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Tunable Photophysical Properties of Thiophene Based Chromophores:
Conjoined Experimental and Theoretical Investigation
Anna Popczyka,b*, Yohan Cheret , Anna Grabarz , Piotr Hanczyc , Piotr Fita , Abdelkrim El-
b
a
c
c
b*
a
a
b
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Ghayoury , Lech Sznitko , Jaroslaw Mysliwiec Bouchta Sahraoui
aFaculty of Chemistry, Wroclaw University of Science and Technology, Wyb. Wyspiańskiego
27, 50-320, Wroclaw, Poland
bLaboratoire MOLTECH-Anjou, UMR 6200, CNRS, UNIV Angers 2 bd Lavoisier, 49045
Angers Cedex, France
cInstitute of Experimental Physics, Faculty of Physics, University of Warsaw, Pasteura 5, 02-
0
93 Warsaw, Poland
*Corresponding authors: anna.popczyk@pwr.edu.pl, abdelkrim.elghayoury@univ-angers.fr
ABSTRACT
In this paper we report synthesis and photophysical properties of six novel thiophene derivatives
(ThD) with D-π-A structure. The subject of this work are three nitrophenyls (1) BT-Th-NO2
and three benzonitriles (2) BT-Th-CN, substituted at different positions of aromatic ring ((a)
ortho-, (b) meta- or (c) para-). Dyes were obtained using simple three-step synthesis and their
1
13
chemical structures were confirmed by H and C NMR, IR as well as high resolution mass
spectrometry. The influence of positional isomerism on optical properties has been explored
experimentally and theoretically. The photophysical properties were investigated using steady-
state as well as time-resolved spectroscopy and the obtained results were supported by
quantum-chemical calculations. TD-DFT calculations indicated that charge-transfer strength
can be correlated with the observed optical properties. In addition, the influence of the acceptor
position on photoluminescence spectra, fluorescence quantum yields and emission lifetimes
was specified. We show that ThD optical properties can be tuned in wide spectral range by the
change made in only single step of synthesis reaction.
Keywords: Thiophene derivatives, charge transfer, push-pull chromophores, quantum yield,
TD-DFT
1

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1
. Introduction
There is a constant need for developing materials for optoelectronic and photonic applications.
Organic molecules stand out among other materials, mostly because of their low-cost synthesis,
non-complicated methods of production and easy way of recycling.1–7 Chromophores multi-
functionality is beneficial trait in wide range of applications spanning from nonlinear optics or
light amplification to energy storage and solar cells technology.8–20 Those desired features are
frequently shown by low-molecular push-pull chromophores containing an electron-donating
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(
D) and electron-accepting (A) groups covalently bonded with a π-conjugated bridge (D-π-A).
Such molecular design supports intramolecular charge transfer (CT) which occurs upon
excitation of the molecule with external light source and can be beneficial for certain nonlinear
optical properties or solar cells manufacture. In present work we show that broadband tuning
of the optical properties is possible by a simple change of the substitution position ((a) ortho-,
(
b) meta- or (c) para-) at the final stage of the ThD synthesis.21–25 It is known that photophysical
properties strongly depend on the nature of the excited-states. The extension of conjugation
influences the separation of excitons that causes fast electron transfer between donor and
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acceptor. Hence, the modification of donor and acceptor moieties, as well as π-conjugated
spacer has a critical impact on CT phenomenon.27–30 Mentioned type of molecules are classified
as diarylethene - where the conversion between two isomers occurs around carbon-carbon
double bond and it can be controlled by external factors i.e. temperature or light. Control over
the isomers conversion can be used in designing molecules for modern technologies such as
all-optical switching or holography.31–37
The influence of electron withdrawing or accepting groups on physicochemical properties of
D-π-A molecules has been widely discussed in scientific literature. Many groups have already
investigated the origin of the heterocyclic ring’s role in photophysical properties by substituting
one of the phenyl ring with different types of cyclic structure such as pyrazoline, pyrole, furan
and dimethoxybenzene.38–45 In this manuscript the main focus is on the impact of structural
isomerism and influence of the excitation-induced CT on the optical properties of D-π-A
molecular systems. We show that simple one step modification in synthesis can lead to
significant change in the optical properties of thiophene derivatives. It should be noted that all
examined compounds contain thiophene (benzothiophene to the lesser extent) as an electron-
donating group and nitrophenyl or benzonitrile as an acceptor groups that exhibit strong
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electron-accepting properties (σ = 0.66 and 0.78 for CN and NO , respectively). We
p
2
emphasize that benzothiophene shows efficient luminescence.47 Moreover, the recent
2

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investigation of cyano and nitro groups’ influence on the solvatochromism of emission put
these compounds as potential candidates for sensors. 48
2
2
. Methods
.1. Experimental section
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In order to confirm the chemical structures of the synthesized products, typical spectroscopic
measurements have been carried out. Nuclear magnetic resonance (NMR) spectra were
obtained on Bruker 300 MHz spectrometer with chemical shifts expressed in ppm (parts per
million), whereas infrared (IR) spectra were measured on Bruker Vertex 70 spectrometer in
-1
range of 400–4000 cm . High resolution mass spectrometry was recorded on Jeol JMS 700
with isobutane as a matrix, using chemical ionisation (CI) method.
2
.2.
Photophysical measurements
Absorption spectra were measured at room temperature in quartz cuvettes by Shimadzu UV
-5
1
800 Spectrometer for solutions of c = 2.40 x 10 M concentration of the dye in chloroform
(
CHCl ) solution. Emission spectra were measured for the same solutions using Shimadzu RF-
3
6000 Spectrofluorometer. For the fluorescence quantum yield (QY) a relative method was used,
with solution of fluorescein in ethanol as a reference. By comparing the area under measured
fluorescence spectra of investigated compounds and reference, estimation of QY comes
straightforward from equation (1),
퐼푠퐴푟푒푓
푛푠2
푛푟푒푓2
훷 = 훷
∗
∗
(1)
푠
푟푒푓
퐼푟푒푓퐴푠
where Φ is fluorescence quantum yield of fluorescein solution, I and I are the integrated
ref
s
ref
areas under the emission spectrum for sample and reference respectively, A and A are the
s
ref
fraction of exciting light which is absorbed at the excitation wavelength in case of sample and
reference and n denotes refractive index of used solvent.
Fluorescence lifetimes were measured using a home-built setup based on PicoQuant HydraHarp
4
00 Multichannel Picosecond Event Timer and two lasers: a picosecond diode laser PicoQuant
LDH-P-C-405B working at 405 nm with repetition frequency set to 5 MHz or a tunable
Ti:Sapphire femtosecond oscillator SpectraPhysics MaiTai with repetition frequency 80 MHz.
In the latter case the laser was tuned to 810 nm and its output was frequency-doubled in a BBO
(
beta-barium borate) crystal to provide excitation at 405 nm. Excitation power at the sample
position was in the range of 0.5 to 25 μW. The sample solution was placed in a 10x10 mm
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quartz cuvette. Experiments were carried out in the L-geometry, with the fluorescence light
collected at the right angle to the direction of the excitation beam. The collected light passed
through a long-pass cut-off filter in order to remove scattered excitation light and through a
o
polarizer with its transmission axis oriented at the magic angle (54.7 ) with respect to the
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polarization of the excitation beam in order to eliminate the influence of rotational diffusion.
The fluorescence light was focused on the entrance slit of a Czerny-Turner monochromator
(
Acton Research SpectraPro 150) used to select a given wavelength from the fluorescence
spectrum. After the monochromator the light was detected with a Hamamatsu R3809U-50
photomultiplier sensitive in the 160–850 nm range. The output signal from the photomultiplier
was amplified with an Ortec Model 9327 amplifier prior to routing to the HydraHarp module.
The overall instrumental response function, measured by scattering the excitation light in a
suspension of titanium dioxide, was narrower than 80 ps full width at half of maximum
(FWHM). The data were analyzed using the DecayFit 1.4 free software [DecayFit -
Fluorescence Decay Analysis Software 1.4, FluorTools, www.fluortools.com]. Fluorescence
lifetimes were estimated through fitting the decay curves with multiexponential decay
functions:
―푡/휏푖
퐼(푡) = ∑ 퐼 푒
(2)
푖
푖
where t is time, I are amplitudes of the decay components, and τ are the decay times of the
i
respective components. The fluorescence quantum yield and the fluorescence lifetimes (the
dominant components) were used to calculate the radiative (k ) and non-radiative (k ) rate
r
nr
constants, with the following system of equations:
1
휏 =
(3)
(4)
푘푟 + 푘푛푟
푘푟
훷 =
푓푙
푘푟 + 푘푛푟
2.3.
Computational details
Within present work we took advantage on Kohn-Sham formulation of Density Functional
Theory (DFT) in order to get insight into electronic structure of examined compounds. All DFT
and TD-DFT calculations were preformed using so-called ultrafine pruned grid. In order to
include solvent effects (chloroform) into computations we used different variants of Polarizable
Continuum Model (PCM).49,50 The linear-response (LR-PCM) variant was used for
optimization and respective frequency calculations, whereas transition energies were
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determined using corrected linear-response (cLR-PCM) scheme.51 The ground-state (GS)
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geometries were optimized using improved thresholds such as, optimization threshold tightened
-5
-10
to 10 au and self-consistent field set to 10 au. Vibrational frequency calculations confirmed
that obtained GS geometries correspond to minima on respective potential energy surfaces.
Examined compounds were expected to exhibit intramolecular charge transfer, thus we choose
computational protocol proven to be efficient for difluoroborates derivatives displaying CT.27,52
In particular, the optimization and subsequent frequency calculations were carried out with
M06-2X/6-31G(d) theory level whereas computations of transition energies were performed
with larger 6-311+G(2d,p) atomic basis set. Finally the charge-transfer parameters (distance
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d , charge q and dipole moment difference in Franck-Condon region μ ) were determined
CT
CT
using Le Bahers approach.53,54 Presented density difference plots have been simulated at LR-
PCM-TD- M06-2X/6-311+G(2d,p) using 0.002 au as a contour value. In these plots red (blue)
orbs indicates increase (decrease) of electron density upon electronic transitions. All described
calculations were performed using Gaussian16 Rev. A.03. 55
3. Synthesis
Commercially available reagents purchased from Sigma Aldrich were used without additional
purification along with the required solvents. Investigated compounds were prepared according
to Horner-Wittig method and all reactions were carried under argon conditions. The synthesis
of intermediate 5-(benzo[b]thiophen-2-yl)thiophene-2-carbaldehyde, as well as the synthesis of
necessary phosphonates was thoroughly described in ESI and supported by NMR
characterization (see ESI S3–S6). Synthesis of presented compounds required only three-step
path to achieve desired thiophene derivatives (Scheme 1). The change of reagents in the last
step allowed to obtain six different compounds characterized by different properties.
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Scheme 1. (a) Synthesis route and (b) chemical structures of investigated compounds.
3.1. Synthesis of (E)-2-(5-(2-nitrostyryl)thiophen-2-yl)benzo[b]thiophene: BT-Th-oNO2
(
1a)
Under argon, in a Schlenk flask, diethyl 2-nitrobenzylphosphonate (0.09 mL, 0.41 mmol) was
dissolved in 5 mL of extra dry DMF, afterwards the mixture was stirred in an icebath. Then
potassium tert-butoxide (0.62 mmol, 1M in EtOH) was added dropwise and the resulting
solution was stirred for 15 minutes. In the second flask a 5-(benzo[b]thiophen-2-yl)thiophene-
2-carbaldehyde (100 mg, 0.41 mmol) was dissolved in 10 mL of extra dry DMF. Afterwards
the potassium (4-cyanophenyl) (diethoxyphosphoryl) methanide from the first flask was added
dropwise and stirred in an icebath for 2 hours. The mixture was then warmed up to room
temperature and stirred overnight. Afterwards the mixture was precipitated with water (50 mL)
and filtered off. After being dried overnight, BT-Th-oNO was obtained as an orange powder
2
1
with 79% yield (118 mg). H NMR (CDCl , 300 MHz) δ/ppm: 8.00 (d, J = 8.2 Hz, 1H), 7.77
3
(
m, 3H), 7.60 (t, J = 7.5 Hz, 1H), 7.48 (s, 1H), 7.46 (d, J = 16.00 Hz, 1H), 7.41 (d, J = 7.2 Hz,
1H), 7.34 (m, 2H), 7.24 (d, J = 3.9 Hz, 1H), 7.21 (d, J = 16.5 Hz, 1H), 7.12 (d, J = 3.8 Hz, 1H).
1
3
C{1H} NMR (125 MHz, CDCl ) δ/ppm: 148.0, 142.1, 140.5, 139.4, 138.0, 137.0, 133.3,
3
1
32.6, 128.9, 128.2, 128.0, 126.7, 125.8, 125.2, 125.03, 125.00, 123.8, 123.3, 122.4, 120.5.
+
HRMS(CI) m/z: [M ] calcd. for C H NO S : 363.0388; found: 363.0389. Selected IR bands
2
0
13
2 2
-1
(cm ): ν = 1600, 1519, 1335, 949, 888, 850, 818.
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3.2.
Synthesis of (E)-2-(5-(3-nitrostyryl)thiophen-2-yl)benzo[b]thiophene: BT-Th-mNO2
(
1b)
BT-Th-mNO was obtained in the same way as BT-Th-oNO compound, using diethyl 3-
2
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nitrobenzylphosphonate instead of diethyl 2-nitrobenzylphosphonate in the first step of
reaction. The final product was a yellow powder and the yield of the reaction was 65% (97 mg).
1H NMR (DMSO-d6, 300 MHz) δ/ppm: 8.45 (s, 1H), 8.08 (d, J = 8.9 Hz, 1H), 8.04 (d, J = 8.1
Hz, 1H), 7.96 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.8 Hz, 1H), 7.74 (d, J = 16.3 Hz, 1H), 7.69 (s,
1
7
1
H), 7.64 (d, J = 8.0 Hz, 1H), 7.44 (d, J = 3.8 Hz, 1H), 7.36 (m, 2H), 7.32 (d, J = 3.9 Hz, 1H),
1
3
.19 (d, J = 16.3 Hz, 1H). C{1H} NMR (125 MHz, CDCl ) δ/ppm: 149.0, 141.9, 140.5, 139.4,
3
38.9, 137.6, 137.1, 132.3, 129.9, 128.9, 126.2, 125.9, 125.1, 125.0, 124.7, 123.8, 122.4, 122.3,
+
120.9, 120.4. HRMS(CI) m/z:[M ] calcd. for C H NO S : 363.0388 Da; found: 363.0384 Da.
2
0
13
2 2
-1
Selected IR bands (cm ): ν = 1619, 1521, 1426, 1350, 957, 887, 866, 845, 826.
3.3.
Synthesis of (E)-2-(5-(4-nitrostyryl)thiophen-2-yl)benzo[b]thiophene: BT-Th-pNO2
(1c)
This compound was synthesized by following the procedure of synthesis for BT-Th-oNO2,
although using diethyl 4-nitrobenzylphosphonate as a starting compound. The final product was
1
an orange powder. The yield of the synthesis was 68% (101 mg). H NMR (CDCl , 300 MHz)
3
δ/ppm: 8.20 (d, J = 8.8 Hz, 2H), 7.73 (m, 2H), 7.58 (d, J = 8.7 Hz, 2H), 7.44 (s, 1H), 7.33 (d, J
= 15.5 Hz, 1H), 7.32 (m, 2H), 7.23 (d, J = 3.8 Hz, 1H), 7.11 (d, J = 3.8 Hz, 1H), 6.92 (d, J =
1
3
1
1
6.00 Hz, 1H). C {1H} NMR (125 MHz, CDCl ) δ/ppm: 146.9, 143.6, 141.8, 140.5, 139.5,
3
38.2, 136.9, 130.0, 129.5, 126.9, 126.3, 126.1, 125.9, 125.1, 124.5, 123.8, 122.4, 120.6. HRMS
+
(
CI) m/z:[M ] calcd. for C H NO S : 363.0388 Da; found: 363.0395 Da. Selected IR bands
2
0
13
2 2
-
1
(cm ): ν = 1585, 1504, 1423, 1337, 965, 947, 888, 868, 845, 824.
3
.4.
Synthesis of (E)-2-(2-(5-(benzo[b]thiophen-2-yl)thiophen-2-yl)vinyl)benzonitrile:
BT-Th-oCN (2a)
Under argon, in a Schlenk flask, diethyl 2-cyanobenzylphosphonate (0.07 mL, 0.41 mmol) was
dissolved in 5 mL of extra dry DMF and the mixture was stirred in icebath. Then potassium
tert-butoxide (0.62 mmol, 1M in ethanol) was added dropwise to the solution and stirred for 15
minutes. In the second flask 5-(benzo[b]thiophen-2-yl)thiophene-2-carbaldehyde (100 mg, 0.41
mmol) was dissolved in 10 mL of extra dry DMF. Afterwards the potassium (4-cyanophenyl)
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(
diethoxyphosphoryl) methanide from the first flask was added dropwise and the whole mixture
was stirred in an icebath for 2 hours. The final mixture was warmed to room temperature and
1
stirred overnight. Yield of the reaction was equal to 84% (118 mg). H NMR (DMSO-d6,
3
00 MHz) δ/ppm: 8.00 (d, J = 8.1 Hz, 1H), 7.94 (m, 1H), 7.82 (d, J = 7.8 Hz, 2H), 7.76 (s,
H), 7.74 (d, J = 16.0 Hz, 1H), 7.69 (d, J = 7.9 Hz, 1H), 7.44 (d, J = 3.9 Hz, 1H), 7.43 (m, 1H),
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1
1
3
7.35 (m, 2H), 7.34 (d, J = 3.9 Hz, 1H), 7.13 (d, J = 16.0 Hz, 1H). C{1H} NMR (125 MHz,
DMSO-d6) δ/ppm: 141.4, 140.1, 139.2, 138.4, 136.7, 135.8, 133.5, 133.3, 130.4, 128.3, 126.54,
1
26.52, 125.47, 125.17, 125.15, 123.9, 123.0, 122.5, 121.0, 117.8, 109.8. HRMS (CI) m/z: [M
+
-1
] calcd. for C H NS : 343.0489 Da; found: 343.0487 Da. Selected IR bands (cm ): ν = 2220,
2
1
13
2
1
617, 1590, 1453, 1425, 983, 938, 888, 826.
3
.5.
Synthesis of (E)-3-(2-(5-(benzo[b]thiophen-2-yl)thiophen-2-yl)vinyl)benzonitrile:
BT-Th-mCN (2b)
BT-Th-mCN was obtained as a yellow powder with 77% yield (109 mg) by using the same
procedure as for BT-Th-oCN compound, only with employing diethyl (3-
1
cyanobenzyl)phosphonate as the starting reactant. H NMR (DMSO-d6, 300 MHz) δ/ppm: 8.11
(
s, 1H), 7.92 (m, 2H), 7.83 (m, 1H), 7.7 (m, 2H), 7.70 (m, 1H), 7.58 (d, J = 17.8 Hz, 1H), 7.45
13
(
d, J = 3.8 Hz, 1H), 7.33 (m, 2H), 7.27 (d, J = 3.8 Hz, 1H), 7.03 (d, J = 16.3 Hz, 1H). C{1H}
NMR (125 MHz, DMSO-d6) δ/ppm: 142.1, 140.1, 138.3, 137.9, 136.1, 135.9, 131.0, 130.9,
30.0, 129.8, 129.1, 126.4, 126.3, 125.1, 125.1, 124.0, 123.8, 122.5, 120.4, 118.8, 112.0. HRMS
1
+
-
(
CI) m/z:[M ] calcd. for C H NS : 343.0489 Da; found: 343.0489 Da. Selected IR bands (cm
21 13 2
1)
: ν = 2226, 1590, 1426, 941, 888, 825.
3
.6.
Synthesis of (E)-4-(2-(5-(benzo[b]thiophen-2-yl)thiophen-2-yl)vinyl)benzonitrile:
BT-TPh-pCN (2c)
This compound was synthesized following the synthesis procedure of BT-Th-oCN, although to
substitute nitryl group in para position, the diethyl (4-cyanobenzyl)phosphonate was used. The
1
final product was obtained as an yellow powder with 69 % yield (97 mg). H NMR (CDCl ,
3
300 MHz) δ/ppm: 7.73 (m, 2H), 7.62 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.43 (s, 1H),
7
.29 (m, 2H), 7.27(d, J = 16.6 Hz, 1H), 7.21 (d, J = 3.8 Hz, 1H), 7.08 (d, J = 3.9 Hz, 1H), 6.86
13
(
d, J = 16.1 Hz, 1H). C{1H} NMR (125 MHz, DMSO-d6) δ/ppm: 142.0, 141.3, 140.1, 138.4,
136.3, 136.1, 132.7, 129.7, 127.1, 126.8, 126.5, 125.20, 125.15, 125.1, 123.8, 122.5, 120.5,
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19.0, 109.5. HRMS(CI) m/z:[M ] calcd. for C H NS : 343.0489 Da; found: 343.0484 Da.
21 13 2
DOI: 10.1039/C9NJ00575G
-1
Selected IR bands (cm ): ν = 2224, 1596, 1425, 961, 945, 887, 861, 816.
4
. Results and discussion
Normalized absorption spectra of all examined derivatives are presented in Figure 1. As can be
seen, absorption band maxima of CN derivatives are localized in a very narrow spectral range
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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0
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9
0
(393–404 nm), whereas respective maxima positions of NO analogues are spanned across five-
2
times wider area (378–424 nm). Although examined compounds differ only in the substitution
position at the acceptor moiety, the (a) ortho- and (c) para-substituted derivatives are
characterized by much broader and rather structureless absorption bands, in comparison with
narrow and well-structured bands of molecules containing the acceptor in (b) meta- position.
As expected, the absorption maxima of (c) para-substituted derivatives (Table 1) are redshifted
with respect to their (b) meta-counterparts. It’s worth mentioning that 1a absorption maximum
is located at a shorter wavelength than that of 1b. Clearly, the absorption bands related to 1
derivatives are the subject of more prominent spectral shifts. In order to explain differences
between spectral features of 1 and 2 quantum-chemical calculations were performed. Firstly,
we checked whether chosen structures (see Scheme 1) are the most stable conformers. Hence
we appointed the other potentially stable conformers to be ones obtained by rotation of the
benzothiophene and/or nitrile or nitro-substituted phenyl ring by 180°. Consequently, full set
of examined structures included 4 conformers for all ortho- and meta-substituted compounds
and 2 conformers for all para- derivatives (see ESI, examined conformers section). Performed
analysis of calculated Gibbs free energies revealed that structures depicted in Scheme~1 are
indeed the most stable conformers of examined compounds. Thus, henceforth we will present
only the data computed for those structures.
Secondly, we calculated vertical excitation energies and compared them with measured
absorption maxima (Table 1). It should be noted that these are not the same physical quantities,
and thus cannot be straightforwardly compared, since one cannot measure vertical transition
energy. However, the vertical approximation is proven to be sufficient in predicting the trends
among the homologous compounds’ series. This in fact is confirmed by discrepancies between
56
Evert and λabs not exceeding 0.2 eV , which prove that this approximation is adequate for our
needs. As can be seen, calculated Evert values reproduce nicely trends observed from experiment
absorption spectra, namely the meta- derivatives are the most blue-shifted, whereas para-
substituted compounds exhibit largest batochromic shifts among both series. Performed
calculations indicate that except of 1a, all absorption maxima correspond to S →S electronic
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transition associated with CT process (see discussion below). Nevertheless, a little more
puzzling situation is observed in case of 1a (ortho-)compound, where one can see strongly
broadened spectra with somewhat two visible peaks, one around 376 nm and the second at
4
04 nm. Indeed, the former peak is more intense which is quite surprising, since it is not
0
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0
consistent with expected trends (ortho-substituted more blue-shifted than meta- derivative), nor
calculated trends. Conducted computation revealed that in case of 1a the latter, slightly less
intense peak is associated with S →S transition characterized with strong CT, whereas
0
1
maximum observed at 376 nm is associated with energetically higher-lying S →S transition.
0
2
Nevertheless, according to calculations, S →S transition should be connected with
0
2
significantly lower peak intensity.
Table 1. Computed vertical excitation energies and absorption maxima measured in chloroform
solution.
Simulations
Evert [nm]
Exp. data
λabs [nm]
(376) 404
393
Compound
f
1
a
385
378
404
378
372
383
1.289
1.428
1.674
1.552
1.590
1.744
1b
1
c
424
397
394
404
2
a
2
b
2
c
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0
Figure 1. Normalized absorption and emission spectra for 1 (a,b) and 2 (c,d).
Table 2. Density difference plots with CT parameters calculated for presented ThDs.
ΔµCT
Compound
1a
Density difference plot
dCT [Å] qCT [e]
[D]
3.49
3.04
0.58
0.49
9.70
7.14
1
b
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1
c
4.34
2.41
0.56
11.60
0
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2
a
0.48
5.27
2
b
2.18
2.89
0.46
0.47
4.64
6.51
2
c
In Table 2 we summarized the outcome of theoretical calculations covering CT-related
parameters and corresponding density difference plots. Obtained results were calculated for the
lowest-lying π→π* transition, which is associated with high oscillator strength (Table 1). As
can be seen, the charge is being transferred mainly from central thiophene ring, acting as
electron donor, to NO /CN acceptor group which confirms the CT nature of the examined
2
transitions. Notably, benzothiophene unit is acting as secondary donor which is most visible in
case of 1c derivative. As expected, the CT strength rises with increase of the distance between
donor and acceptor d . Consequently, (b) meta-substituted derivatives (d =2.18 Å for 2b and
CT
CT
d =3.04 Å for 1b) exhibits weakest CT, while for the (c) para- analogues (d =2.89 Å for 2c
CT
CT
and d =4.34 Å for 1c) CT is the strongest. This statement is confirmed by increase in dipole
CT
moment change values Δμ , which also follow meta<ortho<para order in both series.
CT
However it should be stressed out, that ΔμCT are much larger for nitro-substituted compounds
(
in range of 7.14-11.60 D) than for their nitrile analogues (4.64-6.51 D. Noteworthy, the
presented simulation results reproduce the trends observed for absorption spectra (Figure 1),
since band maxima of 1 (nitrophenyl) derivatives are spanned across much wider range (48 nm)
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than their 2 (benzonitrile) counterparts (7 nm). On other hand, the transferred charge values qCT
are quite similar for all compounds, i.e. for 2 derivatives they oscillate around 0.47 e, while in
case of 1 they vary from 0.49 e to 0.58 e. Notably, the difference between CT strength of 1
(
nitrophenyl) and 2 (benzonitrile) derivatives is also reflected by a change in the size of lobes
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
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3
3
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5
5
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0
1
2
3
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5
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7
8
9
0
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2
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4
5
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9
0
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2
3
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9
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0
depicting electron density difference among acceptor moieties (Table 2). Summarizing all
results presented above, NO derivatives are characterized by much stronger CT character than
2
their CN counterparts. Moreover, the abovementioned results are consistent with the Hammett
substituent constants, according to which NO group is also stronger acceptor than the CN.
2
Worth to mention are strong Stokes shifts visible for every compound, which values vary from
-1
-1
3
000 cm to over 6000 cm , depending on substituent and pattern. For both groups the lowest
value was obtained for the compounds with acceptor moiety attached in b (meta-) position.
Surprisingly, the highest Stokes shift values among molecules with cyano substituent was
observed for 2a (ortho- position), whereas for the NO series it was, as predicted, 1c (para-
2
position). The theoretical findings, explaining the quantum-chemical background of
investigated molecules photophysics are in good accordance with the experimental data (c.f.
Table 3).
Table 3. Main photophysical parameters for synthesized compounds measured in chloroform
λ
nm]
fl
-1
-1
Δν [cm-1]
8
-1
9
-1
Comp
λ
abs [nm] ε[M cm ]
Φ
fl
τ
i
[ns]
k 10 [s ] k 10 [s ]
r
nr
[
0
2
.55 (0.905)
1
a
376
393
424
397
394
404
31800
48000
38500
41600
67700
60800
466
447
572
480
465
485
5136
<10-2
<10-3
0.15
0.15
0.22
0.18
-
-
-
-
.1 (0.095)
b
0
.033 (0.979)
0.44 (0.019)
.4 (0.002)
1
b
3074
6102
4356
3857
4134
4
c
0
.20 (-0.180)
1
c
1.3
0.75
1
0
.14 (0.820)
.19 (0.905)
7.1a
4.0a
2
a
0.44 (0.094)
6.0 (0.001)
0.47 (1.000)
14 (<0.001)
0.29 (0.992)
1.7 (0.006)
6.1 (0.002)
2
b
4.7
6.1
1.7
2.8
2c
λ
abs– absorption maxima λfl – fluorescence maxima, Δν – Stokes shift , Φfl – fluorescence quantum yield calculated
-5
in reference to fluorescein (2.0  10 M, EtOH), τ
i
– fluorescence decay components (dominant component printed
in bold) with their respective contribution, k
r
– radiative rate constant (calculated from the dominant component,
except 2a), knr – non-radiative rate constant.
a
b
c
calculated from the weighted average of two dominant components (avg = 0.213 ns), shorter then IRF, raise
of the fluorescence intensity
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In case of fluorescence measurements, 1 compounds exhibit emission maxima at λ = 466 nm,
em
λem = 447 nm and λem = 572 nm for 1a, 1b, 1c derivatives respectively. On the other hand, 2
fluorescence maxima are localized at λ = 480 nm, λ = 465 nm and λ = 485 nm for 2a, 2b,
em
em
em
2
c respectively. In both groups fluorescence maxima are located at the shortest wavelengths for
0
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acceptors at the meta- position, whereas the largest redshifts are visible for acceptors at the
para- position (c). Surprisingly, the fluorescence quantum yield is the highest for 2b, whereas
for both 2a and 2c fluorescence quantum yields have similar values (~16%). Nitro-substituted
molecules (group 1), exhibit lower fluorescence intensity than their cyano counterparts
(group 2). As presented in Table 3, molecules substituted at ortho- (1a) and meta- (1b) positions
show negligible fluorescence intensity, whereas for 1c (para- position) it is over hundred times
higher.
Fluorescence decay curves recorded in chloroform (Figure 2) revealed complicated behavior of
fluorescence in both groups of molecules. For all compounds two or three decay components
were necessary to reproduce the experimental kinetics. It should be noted that for molecules 1b
and all 2 the longest component (in the nanosecond range) has the relative amplitude of the
-3
order of 10 which is attributed rather with the impurities or products of photodecomposition
than to the synthesized molecules intrinsic properties.
Fluorescence decays for 2b and 2c (Figure 2b) can be considered to be mono-exponential with
the fluorescence lifetimes equal to 0.47 and 0.29 ns respectively. For these molecules time-
resolved fluorescence measurements do not suggest any excited-state processes nor presence of
various isomers in the solutions. In contrast, the pair of molecules substituted at the –ortho
position (1a, 2a) exhibits two non-negligible decay components, with the slower one
contributing approximately 10% of the overall fluorescence decay. In this case a presence of
two emitting species could be suspected, however it is not supported by steady-state absorption
and fluorescence spectra.
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Figure 2. Fluorescence decay curves for (a) 1a-c (recorded with excitation by the picosecond
diode laser) and (b) 2a-c (recorded with the femtosecond laser used for excitation) families of
compounds recorded in CHCl , at room temperature, for excitation wavelength λ = 405 nm.
3
The most complicated behaviors are observed for 1b and 1c. The fluorescence decay recorded
for 1b contains a very fast component, whose decay time is significantly shorter than the width
of the instrumental response function of the apparatus used and thus it could not be reliably
determined. The second component has the decay time similar to fluorescence lifetimes of other
molecules (0.44 ns) and contributes approximately 2% of the fluorescence decay. Such behavior
indicates that the fluorescence of the primarily excited form is very efficiently quenched, as
confirmed by its very low quantum yield. The longer decay component can be attributed to a
fluorescent photoisomer formed in the excited state with a low yield in an isomerization process
competing with the radiationless deactivation.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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0
The last molecule - 1c, is the only one where a fast (0.2 ns) raise of the fluorescence intensity
is followed by a relatively slow (1.14 ns) decay. It indicates a process in the excited state of 1c,
which leads to formation of longer-lived fluorescent species. However, in contrast to 1b the
,
primarily excited form is not deactivated efficiently, and the product is produced with a high
yield. The structure of the molecules and the results of quantum chemical calculations suggest
that charge transfer and isomerization by rotation around the double carbon bond can be
involved in the excited-state processes. Nevertheless, the exact identification of these processes
requires further photophysical studies of the synthesized compounds.
For molecules whose fluorescence originates mainly from a single species radiative and non-
radiative transition rate constant were calculated using relationships between fluorescence
quantum yields and fluorescence lifetimes (See eq. (3) and eq. (4)). In every case the non-
radiative rate constant is several times higher than the radiative rate constant. Both values are
visibly lower for 1c than for molecules of the 2 group. This might be due to the stronger
intramolecular charge transfer occurring in the molecule with the nitro group.
5
. Conclusions
In this work we present synthesis of six novel thiophene derivatives combined with their
photophysical properties characterization. The compounds were characterized with steady-state
and time-resolved spectroscopic techniques and the experimental results were supported by
quantum chemical calculations. We showed that molecules with the acceptor substituted in
different positions exhibit diverse photophysical features. Quantum chemical calculations
1
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DOI: 10.1039/C9NJ00575G
confirmed that observed differences in spectral properties of absorption are directly connected
with changes in the strength of the transitions CT character. Therefore (b) meta-substituted
derivatives manifesting moderate CT are characterized with well-structured, narrow absorption
spectra, while bands of (a) ortho- and (c) para- analogues, displaying much stronger CT
character, are red-shifted, broad and rather structureless. Quite similar features are observed in
emission spectra. Nevertheless, interpretation of fluorescence-related parameters tends to be
more puzzling. Although we observe significant enhancement of QY (especially for ortho- and
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meta- derivatives) when replacing NO acceptor with CN group, there is no systematic
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relationship between QY values and the acceptor substitution position. However, in 1 series,
change of acceptor substitution position from para- to ortho- and/or meta- resulted in almost
complete fluorescence quenching. We proved that by simple modification in the molecular
structure, made in the last synthesis step, the photophysical properties can be significantly
tuned. Such behavior is beneficial and makes the prepared compounds as valuable candidates
for applications in organic electronics and photonics. To summarize, we synthesized and
characterized thiophene derivatives. Dyes can be obtained using simple synthesis protocol with
high reaction yields and their optical properties can be tailored in broad spectral range through
the constitutional isomerism in one reaction step.
Corresponding authors
*
*
E-mail: anna.popczyk@pwr.edu.pl
E-mail: abdelkrim.elghayoury@univ-angers.fr
Notes
The authors declare no competing financial interest.
Author Contributions
The manuscript was written through contributions of all authors. All authors have given
approval to the final version of the manuscript. All authors contributed equally.
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Synthesis and theoretical investigation of six donor-acceptor thiophene based derivatives with
tunable photophysical properties.
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