Synthesis, photophysical and electrochemical properties of symmetric silicon-linked coumarin-oxadiazole derivatives

Article abstract of DOI:10.1016/j.tet.2016.09.033

A novel, silicon-linked, symmetric, V-shaped, coumarin derivative (1) with an electron-deficient 1,3,4-oxadiazoles unit and a phenyl moiety was synthesized and characterized. An efficient multifunctional organic light-emitting diode material was obtained

Full text of DOI:10.1016/j.tet.2016.09.033

Accepted Manuscript
Synthesis, photophysical and electrochemical properties of symmetric silicon-linked
coumarin-oxadiazole derivatives
Lingling Zhang, Yan Xia, Min Li, Dongfeng Li, Ruibin Hou
PII:
S0040-4020(16)30949-8
10.1016/j.tet.2016.09.033
TET 28104
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 13 July 2016
Revised Date: 9 September 2016
Accepted Date: 18 September 2016
Please cite this article as: Zhang L, Xia Y, Li M, Li D, Hou R, Synthesis, photophysical and
electrochemical properties of symmetric silicon-linked coumarin-oxadiazole derivatives, Tetrahedron
(2016), doi: 10.1016/j.tet.2016.09.033.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
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ACCEPTED MANUSCRIPT
Graphical Abstract
Toluene
Chloroform
Acetone
1000
800
600
400
200
0
Acetacitrile
Dimethyl sulfoxide
a
b
c
d
e
4
50
500
550
600
650
Wavelength(nm)

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Synthesis, photophysical and electrochemical properties of
symmetric silicon-linked coumarin-oxadiazole derivatives
a
a
c
a,*
a,b,*
Lingling Zhang , Yan Xia , Min Li , Dongfeng Li , Ruibin Hou
a
School of Chemistry and Life Science, Changchun University of Technology, Changchun 130012, P. R. China
b
Advanced Institute of Materials Science, Changchun University of Technology, Changchun 130012, P. R.China
c
College of Materials Science Engineering, Jilin University, Changchun 130012, P. R.China
ABSTRACT
A novel, silicon-linked, symmetric, V-shaped, coumarin derivative (1) with an electron-deficient
1,3,4-oxadiazoles unit and a phenyl moiety was synthesized and characterized. An efficient
multifunctional organic light-emitting diode material was obtained through the use of optical,
electrochemical, thermal, and theoretical investigations. We show that the Si atom induces a
V-shaped structure that weakens π-π stacking and thus limits aggregation-induced quenching. As
expected, a gradual transition from a locally excited state to a intramolecular charge-transfer state
is observed with increasing solvent polarity. This new type of compound exhibits tunable light
emission in solution making it a versatile emitter.
Keywords: V-shaped, Coumarin, 1,3,4-oxadiazole, Emitter
*Corresponding authors. Tel: +86 431 85716671 (R. Hou)
E-mail addresses: hrb1018@163.com (R. Hou), lidongfeng@mail.ccut.edu.cn (D. Li).
1

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1
. Introduction
Luminescent organic materials have been widely used as active elements in optoelectronic
1
-6
devices, chemosensors, bioprobes, and organic light-emitting diodes. Most of these fluorescent
organic molecules, however, exhibit planar and well-conjugated structures with reasonable
emission in dilute solutions and weak or nonexistent emission in the solid state owing to
7-10
aggregation-caused quenching.
Recently, research has focused on reducing
aggregation-induced quenching in the solid state to produce organic molecules capable of forming
highly luminescent films. Multiple groups have independently reported an interesting
phenomenon where in aggregated molecules are able to fluoresce more intensely than their dilute
solutions. This observation has been explained in terms of the unique phenomenon of
11,12
aggregation-induced emission (AIE).
Propeller-shaped molecules such as tetraphenylethene,
hexaphenylsilole, and quinoline-malononitrile as well as their derivatives, are known for their
13-25
unique ability to promote AIE.
Recently, a new V-shaped compound has displayed tunable
2
6, 27
light emission in solution and the solid state.
Additionally, the integration of intramolecular
charge transfer (ICT) and AIE into one compound has led to a new phenomenon: strong
fluorescence not only in dilute solutions but also in the solid state or aggregated forms. For
instance,
Zhu
and
co-workers
reported
a
new
donor–acceptor
system,
tetraphenylethene–naphthalimide, which displayed dual photoluminescence activity from both
5
ICT and AIE. However, the integration of ICT and AIE into one molecule is still rare and not well
understand and thus warrants further study to understand the relationship between molecular
structure and optical properties. In particular, investigations about how molecular geometry and
intermolecular distances affect fluorescence are rare. This gap in the literature along with the
2

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above-discussed recent advances inspired us to develop a new V-shaped fluorescent molecule with
tunable light emission both in solution and in the solid state.
In recent years, organosilicon compounds have become the focus of several research efforts
after recent reports indicate that organosilicon compounds, especially siloles, have excellent
28
emission properties. Si-based tetrahedral organic molecules and polymers have been intensively
investigated as electroluminescent materials. For example, Liu and co-workers recently reported a
2
9,30
series of tetrahedral luminescent materials comprising SiAr cores . They found that their
4
fluorene derivatives were efficient blue light-emitting materials and that Si-centered materials
were with good film-forming ability and quantum efficiency. One noteworthy feature of
3
0
Si-centered tetrahedral materials is their high PL efficiency (nearly 100%). We have recently
reported a series of tetrahedral luminescent materials comprising SiAr Me cores where the Si atom
2
2
possesses a special V-shaped structure that exhibits tunable light emission in solution and in a
27
solid-state thin film. In a continuation on our research on V-shaped luminescent materials, herein
we report the development of novel V-shaped fluorescent molecule containing
a
coumarin-1,3,4-oxadiazole and a Si core atom. We chose coumarin as a building unit because of
its well-established good luminescent properties as well as its wide application in chemosensors,
light-harvesting molecular arrays, photovoltaics, and particularly in organic light-emitting
3
1-34
diodes.
coumarin-containing emitters to exhibit strong intermolecular interactions in the solid state, which
causes aggregation-induced quenching. We found that our new V-shaped
Coumarin moieties’ strong tendency to π−π stack, however, generally leads
coumarin-1,3,4-oxadiazole derivative, however, does not suffer from this quenching mechanism as
it exhibits strong and tunable light emission in solution and in the solid state.
3

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Scheme 1. Synthetic routes to the target compound 1.
2
. Results and discussion
2.1. Synthesis and characterization
The synthetic procedure for target compound 1 is summarized in Scheme 1, and the detailed
procedures are given in the experimental section. An important intermediate, silylbenzohydrazide
moiety (5), was prepared quantitatively by the reaction of 4 with excess amounts of hydrazine
monohydrate under reflux conditions. Finally the reaction of 5 and coumarin acid (7) in
phosphoryl chloride as the refluxing solvent eventually produced compound 1. The structure of 1
1
13
was characterized by H and C NMR spectroscopy, mass spectra, and elemental analysis (see the
Supporting Information).
Colourless crystals suitable for an X-ray diffraction study of the key precursor 5 was obtained
by slowly evaporating CH Cl /hexane solutions of 5 at room temperature. Its crystal structures
2
2
was determined by X-ray crystallography at room temperature revealing that compound 5
crystallizes in the monoclinic system with a space group of P2/n (Table S1). As shown in Fig. 1.
In the crystal structure of compound 5, the two phenyl moieties are both nearly planar and form a
4

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dihedral angel of 89.97 (±1). Additionally, the molecule is composed of a V-shaped building unit
separated by a silicon atom.
Crystallographic data for the structure of 5 has been deposited with the Cambridge
Crystallographic Data Centre as supplemental publications CCDC 1489385 .
Fig. 1. Crystal structures of the key precursors 5. Thermal ellipsoids are drawn at the 30% level.
2.2. Photophysical and electrochemical properties
The ultraviolet-visible absorption and photoluminescence spectra of 1 in CHCl are displayed
3
in Fig. 2. The three major absorption peaks located at 247, 284 and 432 nm originate from the
π-π* absorption of the conjugated coumarin-phenyl 1,3,4-oxadiazole moiety. The shoulder peak at
4
1
48 nm can be attributed to the ICT transition character from the diethylamino to the
,3,4-oxadiazole. The ICT transition was further confirmed by fluorescence spectra in solvents of
varying polarity with the same concentration. These results are shown in Fig. 3. The emission
peaks (λ ) are generally red shifted from λ=469 nm in toluene to λ=496 nm in DMSO. The
em
bathochromic shift, combined with the decreased quantum yield (QY), can be ascribed to
2
6
stabilization of the excited state. This behavior originates from the ICT effect. From the
absorption edge of the ultraviolet-visible spectrum, the optical band gap (E ) of 1 is estimated to
g
be 3.47eV. 1 exhibits broad and structureless emission bands with peaks at 474 nm in CHCl . The
3
5

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emission spectra, however, were different between the solution and film samples with regard to the
broad emission peaks and red-shift shown in Fig. 2. The fluorescence QY of 1 measured at room
temperature in dilute CHCl was moderate compared with the PL intensity of a standard solution
3
37
of quinine sulfate (QY=0.54). The photoluminescence quantum efficiency of the films was
measured by the integrating sphere method (Table 1).
UV-vis CHCl
1.0
0.8
0.6
0.4
0.2
0.0
3
PL CHCl
PL film
3
250 300 350 400 450 500 550 600 650 700 750
Wavelength (nm)
Fig. 2. UV–vis absorption and PL spectra of 1. Inset 1 Photographs of the ground powder under under 365 nm
illumination.
Toluene
1000
Chloroform
Acetone
800
600
400
200
0
Acetonitrile
Dimethyl sulfoxide
a
b
c
d
e
450
500
550
600
650
Wavelength(nm)
-
5
Fig. 3. PL spectra of 1 (1×10 mol/L) in different solvents with varying polarities. Excitation wavelength = 432nm.
Insets show luminescence photographs of 1 in toluene(a), chloroform(b), acetone(c), acetonitrile(d), dimethyl
sulfoxide (e) under 365 nm illumination.
6

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The electrochemical properties of 1 in DMF were investigated by cyclic voltammetry (CV). The
electrochemical data are displayed in Table 1. Fig. 4 displays representative CV traces for the
oxidation and reduction of 1. CV analyses reveal that 1 undergoes a quasi-reversible reduction at
the cathodic potential associated with the reduction of the electron-deficient oxadiazole moiety to
form ananion radical. 1 exhibits an irreversible oxidation processes corresponding to the removal
of electrons from the terminal 7-diethylaminocoumarin group, resulting in radical cations.
-5
-5
-5
2.0x10
-6
6
4
2
.0x10
.0x10
.0x10
1.0x10-6
0.0
-
1.0x10-6
-
2.0x10-6
-3.0x10
-6
-
-
-
-
4.0x10
-6
5.0x10-6
6.0x10-6
7.0x10-6
-8.0x10-6
-
9.0x10
-6
-0.5
0.0
0.5
1.0
E(V) vs Ag/AgCl
0.0
-
5
-
2.0x10
4.0x10
-5
-
-1.5
-1.0
-0.5
0.0
E(V) vs Ag/AgCl
0.5
1.0
-
3
Fig. 4. Cyclic voltammograms of 1 in DMF (1×10 M). (inset: DPV of 1 under the same conditions).
Table 1 Photophysical, physical, and electrochemical data
a
a
b
c
d
red/peak
ox/peak
e
opt
Compound
Amax,Abs(nm)
λmax, em(nm)
λmax,em(n)
ΦF
ΦF
E
/V
E1
/V
Eg
1
432.3
474.5
538.6
0.65 18.6
-0.56
0.86
3.47
a
Measured in CHCl3
Measured in film
b
c
d
e
37
Measured in CHCl with quinine sulfate as the standard (QY = 0.54)
3
The photoluminescence quantum efficiency of the films was measured by the integrating sphere method
abs
onset
Calculated using Eg = 1240/λ
2
.3. Thermal properties
The thermal properties of 1 were investigated by thermal gravimetric analysis and differential
scanning calorimetry under a nitrogen atmosphere. As shown in Fig. 5, the decomposition
7

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temperature (T , corresponding to a weight loss of 5%) is 398°C. The glass transition temperature
d
(Tg) of 126 °C was also obtained from Fig. 5. The excellent thermal stability of 1 would benefit
the forming of amorphous films.
120
110
100
90
80
70
60
50
40
30
4
3
3
2
2
1
1
0
.0
.5
.0
.5
.0
.5
.0
.5
Tg
0.0
100
150
200
250
Temperature (°C)
100
200
300
400
500
Temperature (°C)
Fig. 5. Thermal gravimetric analysis traces and differential scanning calorimetry thermograms of the 1.
2
.4 Density functional theory calculations
3
8
All calculations were carried out using the Gaussian 09 (G09) package. Calculations on the
electronic ground state of complex 1 were carried out using density functional theory (DFT) with
3
9-41
42
Becke’s LYP exchange-correlation functional
together with the 6-31G basis set. GaussView
5.0.8 was used for the visualization of the structures and for orbital manipulations.
To gain insight into the photophysical behavior of all of the studied complexes, DFT was used
to simulate 1’s molecular orbitals. To understand the charge carrier injection barriers, we
investigated the changes that took place upon frontier orbital substitution. The highest occupied
molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) orbitals and the
e
energy gap of 1 are displayed in Fig. 6. These results, especially the calculated energy gap ( E =
g
e
opt
3
.67eV), largely agree with the experimental photophysical data ( E = 3.47eV), which suggests
g
that the DFT calculations can to a certain degree be used to predict the photophysical behavior of
8

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these complexes. The S1 state resulted from the HOMO→LUMO excitation (Fig. 6), which is
assigned as charge transfer from the diethylamino the 1,3,4-oxadiazole moiety.
-
2.0
2.5
LUMO
-2.31
-
3.67
-
6.0
6.5
HOMO
-5.98
-
Fig. 6. Electron density contours and orbital energies calculated for the HOMO and LUMO of 1 at the Becke’s
LYP/DZP level in CH Cl .
2
2
The calculated vertical ionization potential IP (IP ), adiabatic IP (IP ), vertical electron affinity
v
a
(
EA ), and adiabatic EA (EA ) were listed in Table 2. The reorganization energy (λ) can be used to
v
a
estimate the charge transport rate and the balance between holes and electrons. These results were
listed in Table 2. The reorganization energy for electron transport can be expressed in terms of the
electron extraction potential (EEP): λ = EEP − EA . The EEP is the energy difference between M
e
v
-
−
and MM (anionic) when considering M geometry. Likewise, the reorganization energy for hole
transport can be expressed in terms of the hole extraction potential (HEP): λ = IP − HEP. The
h
v
+
+
HEP is the energy difference between M and MM (anionic) when considering M geometry. We
found that complex 1 had similar electron and hole transfer ability. Thus, 1 may be a good
luminescent organic material.
9

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Table 2. Ionization potentials, electron affinities, extraction potentials, internal reorganization energies and Δ
=
∣λ –λ ∣ (in eV) for these studied complexes.
ih ie
IPv
IPa
HEP
6.19
EAv
0.66
EAa
0.88
EEP
1.68
λih
λie
Δ
1
7.38
6.33
1.19
1.02
0.16
3. Conclusions
We developed a facile and effective method for the synthesis of a novel, V-shaped organic
fluorescent compound. A central Si atom was used to disrupt the aggregation of coumarin moieties,
thus preventing aggregation-induced quenching and resulting in a QY of 18.6% in the solid state.
The lack of solid-state aggregation was verified by its spectral similarities in solution and as a film.
This novel emitter is solution processable and exhibits good film-forming ability and high thermal
stability and could be a potential emitter.
4
. Experimental
2. 1. General
NMR spectra were recorded in CDCl with a Bruker AV-400 Spectrometer and chemical shifts
3
were referenced relative to tetramethylsilane (δH/δC=0). IR spectra were recorded on a
Perkin Elmer 2400 instrument (KBr pressed disc method).The mass spectra were
performed on a Shimadzu MALDI AXIMA-CFRþ spectrometer. Elemental analysis was
performed on an Elementar Vario EL CHN elemental analyzer. Ultraviolet-visible (UV-vis)
spectra were recorded on a Lambda 25 spectrophotometer in CHCl . Fluorescence spectra were
3
obtained from a Shimadzu RF-5301PC fluorescence spectrophotometer in CHCl The absolute
3
.
fluorescence quantum yields (Φf) were measured in an integrating sphere system. Cyclic
voltammetric studies were carried out using a CHI 852C instrument with CH Cl as the solvent
2
2
-3
(
10 M) and 0.1 M Bu ClO as the supporting electrolyte. Counter and working electrodes
4 4
1
0

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consisted of a Pt wire and a Pt disk, respectively, and the reference electrode was Ag/AgCl. The
thermal stability of the target compounds was characterized using a Shimadzu DTG-60H
thermogravimetric analyzer. Starting compounds 2-7 were synthesized according to literature
35, 36
method.
2
.2. Synthesis of
p, p’-{Bis[2-(7-Diethylaminocoumarinyl)-1,3,4-oxadiazol-5-yl]diphenyl}dimethylsilane
A mixture of 7-(N,N′-diethylamino)-coumarin-3-carboxylic acid (3.86 g, 14.8 mmol),
4,4’-dihydrazidediphenyldimethylsilane(2.43 g, 7.39 mmol) and phosphorous oxychloride (26 mL)
was heated at reflux for 6 h, and then poured onto crushed ice after cooling to room temperature.
The dark green solid precipitate was filtered and washed thoroughly with distilled
Water. After silica gel column chromatography (EA/CH Cl , 1/1, v/v), an orange red
2
2
solid was obtained. The solid was recrystallized from THF obtained the pure final compound
1
(
2.59 g,). Yield: 45%. M.p. 155.31 °C (DSC). H NMR (400 MHz, CDCl ) δ: 0.64 (s, 6H), 1.25 (t,
3
J = 7.2 Hz, 12H), 3.46 (q, J = 7.2 Hz, 8H), 6.53 (d, J = 2.4 Hz, 2H) , 6.65 (dd, J = 8.8 Hz, 2H),
13
7
.41 (d, J = 8.8 Hz, 2H), 7.67 (d, J = 8.0 Hz, 4H) , 8.15 (d, J= 8.0 Hz, 4H), 8.51 (s, 2H); C NMR
(
100 MHz, CDCl ) δ: -2.59, 12.54, 45.20, 97.09, 103.77, 107.98, 109.92, 124.74, 126.32, 130.73,
3
-
1
1
1
7
34.75, 142.22, 144.90, 152.71, 157.70, 157.92, 162.24, 164.63; FT-IR (KBr, cm ): 2972, 2918,
+
733, 1623, 1596, 1533, 1415, 1228, 814; C H N O Si calculated for [M+H] 778.94, found
4
4
42
6
6
79.33.
Acknowledgements
This work was supported by the National Science Foundation of China (No. 21442004),
The education office of Jilin provincial (grant No. 2016320).
11

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ACCEPTED MANUSCRIPT
Highlights
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We report the synthesis of symmetric silicon-linked, symmetric, V-shaped, coumarin
derivatives 1 with electron-deficient 1,3,4-oxadizoles unit.
The integration of AIE and intramolecular charge transfer (ICT) can be in one
compound 1.
This kind of material can emit strong fluorescence not only in the solid state or
aggregation forms, but also in dilute solutions.