Controllable supramolecular architectures for modulating optical properties on the molecular aggregation level

Article abstract of DOI:10.1002/ejoc.201402460

Driven by the association of chemical weak forces and solvent effects, zero- to two-dimensional nanostructures of thiophene-substituted perylene bisimide such as spheres and blocky structures were obtained. Light-controlled intramolecular charge transfer from the trithiophene unit to the perylene bisimide in the solid state can induce a hypochromatic shift and enhanced fluorescent emission.

Full text of DOI:10.1002/ejoc.201402460

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FULL PAPER
DOI: 10.1002/ejoc.201402460
Controllable Supramolecular Architectures for Modulating Optical Properties
on the Molecular Aggregation Level
Runsheng Jiang,[a,b] Zheng Xue,[c] Yongjun Li,*[a] Zhihong Qin,[a,b] Yuliang Li,*[a] and
Daoben Zhu[a]
Keywords: Conjugation / Nanostructures / Nanoparticles / Charge transfer / Solid-state structures
Driven by the association of chemical weak forces and sol-
vent effects, zero- to two-dimensional nanostructures of thio-
phene-substituted perylene bisimide such as spheres and
blocky structures were obtained. Light-controlled intramo-
lecular charge transfer from the trithiophene unit to the per-
ylene bisimide in the solid state can induce a hypochromatic
shift and enhanced fluorescent emission.
the π-conjugation either along the long molecular axis from
perylene to hexarylene diimides, which induces a significant
bathochromic shift, or along the short axis at the bay posi-
tions of the aromatic core, resulting in a hypsochromic
shift.[13] Understanding the structure–property relation-
ships that relate specifically to aggregate nanostructures
and materials is critical for the development of new archi-
tectures for benign, high-performance conjugated mol-
ecules.[14,15]
To derive different properties from individual molecules,
tuning the self-assembly process is an effective method.[16]
The optical properties of the conjugated molecules can also
be influenced by different conformations and spatial arran-
gements, such as observed in conformation-dependent
fluorescent enhancement induced by laser irradiation.[17]
Here, we report a PDI derivative bridged by trithio-
phenes that shows a hypochromatic shift and fluorescent
enhancement upon UV light irradiation on the aggregated
level. The changes are realized by tuning the intramolecular
Introduction
In recent years, perylenetetracarboxylic acid diimides
(PDI) have been extensively studied as building blocks for
functional supramolecular architectures through hydrogen
bonding, metal ion coordination, and π–π stacking interac-
tions.[1] Due to their outstanding optical and electronic
properties, especially upon formation of aggregated nano-
structures,[2] PDI has been widely used for electronic mate-
rials,[3] organic solar cells,[4] photoluminescence,[5] sensors,[6]
organic light-emitting diodes,[7] field-effect transistors,[8] dye
lasers,[9] liquid crystalline materials,[10] and molecular
switches.[11] In particular, there is growing interest in the
design of PDI systems that can self-assemble into uniform
aggregates with specific shape and novel functionalities. In-
deed, an effective way to shape supramolecular architec-
tures is through molecular self-assembly technology based
on intramolecular, intermolecular, and molecule-substrate
interactions.
With the aim of improving the performance of PDI as a
functional material in devices, a great deal of interest has
been stimulated in the past decade in modifying PDI mol-
ecules to tune the photophysical and redox properties of the
systems and to enhance their ability to self assemble.[12]
Such molecular modification can be achieved by expanding
[a] Beijing National Laboratory for Molecular Sciences (BNLMS),
CAS Key Laboratory of Organic Solids, Institute of Chemistry,
Chinese Academy of Sciences,
Beijing 100190, P. R. China
E-mail: ylli@iccas.ac.cn
liyj@iccas.ac.cn
http://www.iccas.ac.cn
[b] GraduateUniversity of Chinese Academy of Sciences,
Beijing 100049, P. R. China
[c] State Key Laboratory for Supramolecular Structures and
Materials, College of Chemistry, Jilin University,
Changchun 130012, P. R. China
Figure 1. Schematic interpretation of the hypochromatic shift and
enhanced emission observed in thiophene-bridged perylene bis-
imide supramolecular architectures.
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201402460.
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charge transfer (ICT) from the trithiophene unit to the per- arises from the thiophene units, and the peak at 540 nm
ylene bisimide through light-induced conformation changes originates from the PDI units. Particularly in the concentra-
of the trithiophene moieties (Figure 1).
tion range of 0 to 1ϫ10–6 m, the emission of PDI unit was
quenched due to ICT from the trithiophene unit to the per-
ylene bisimide. When the concentration was higher than
1ϫ10–6 m, although the emission of thiophene units
(409 nm) started to decrease due to stacking effects, the
emission of the PDI units (540 nm) appeared, because the
aggregation-induced emission effect (AIE) of the perylene
bisimide unit compensates for the ICT from the tri-
thiophene unit to the perylene bisimide (Figure 3).
Results and Discussion
As shown in Scheme 1, the Suzuki reaction of 1-bromo-
perylenetetracarboxylic acid diimide and 2,2Ј-trithiophene-
5,5Ј-diboronic acid bis(pinacol) ester smoothly afforded
thiophene-substituted compound 2 in 60% yield upon heat-
ing to reflux overnight. Compound 2 was characterized by
1H NMR, 13C NMR and high-resolution MALDI-TOF
MS analyses.
The measured redox potentials for thiophene-substituted
perylene are shown in Table S1 (see the Supporting Infor-
mation). Compound 2 exhibits two reversible one-electron
oxidation peaks at 1.19 and 1.43 V. The first oxidation po-
tential of 2 is 0.53 V lower than that of the parent PDI,
indicating that attachment of the trithiophene group to the
perylenetetracarboxylic acid diimide makes the molecule
easier to oxidize. Compound 2 shows two reversible re-
duction potentials at –0.56 and –0.80 V (vs. SCE), and no
significant shift was observed compared with the parent
PDI. From the HOMO (–5.59 eV) and LUMO (–3.84 eV)
energy levels and the corresponding energy gap (1.75 eV),
the π-electron-rich thiophene unit effectively extends the π-
conjugation system of 2, raising the HOMO level and leav-
ing the LUMO level unchanged, resulting in a smaller en-
ergy gap compared with that of the parent PDI (2.15 eV).
The absorption and fluorescence spectra of 2 in dichloro-
methane (CH2Cl2) at room temperature are shown in Fig-
ure 2, which reveals the perylene core π–π* transition ab-
sorption bands around 510 nm (εmax = 26400 m–1 cm–1) and
thiophene unit absorption at 378 nm, as well as a shoulder
charge-transfer band around 550–700 nm (the latter band
does not change with concentration, see Figure S3 in the
Supporting Information). Compared with the parent PDI
Figure 2. Absorption and emission (excited at 480 nm) spectra of
2 and PDI in CH2Cl2 (1ϫ10–6 m) at room temperature.
Figure 3. Emission spectra (excited at 360 nm) of 2 in CH2Cl2 at
different concentrations.
To study the aggregation ability of 2 (which dissolved in
(λmax = 528 nm), the maximum absorption value of 2 CH2Cl2 at a concentration of 1.0ϫ10–4 m), self-assembly
showed a blueshift of 18 nm. Excitation at the absorption was carried out in a range of solvents such as hexane or
band of the perylene bisimide unit led to emission at acetone after optimization. Typical SEM and TEM images
572 nm, with a fluorescence quantum yield of 0.37. The of the nano- and micro-aggregate structures of 2 with dif-
emission spectra of 2 excited at the thiophene unit (360 nm) ferent morphologies are shown in Figure 4. Self-assembly
are shown in Figure 3, which reveals two clear fluorescent in CH2Cl2/hexane leads to regular nanospheres (Figure 4a).
emissions (430 and 540 nm). The emission peak at 430 nm The SEM images of 2 (Figure 4c) assembled in CH2Cl2/
Scheme 1. Synthesis of the thiophene-substituted perylene diimide.
2
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Controllable Supramolecular Architectures
acetone (1:1, v/v) show a highly regular blocky structure which indicated that H-type aggregation occurred in the
with approximately 3 μm length and 400 nm thickness (Fig- blocky structures (Figure 4e).
ure S4); its TEM images are shown in Figure 4d.
The optical properties of these nanostructures prepared
from 2 were further studied with a laser scanning confocal
microscope (LSCM). Nanostructures of 2 showed weak so-
lid emission around 750 nm, which is related to the charge-
transfer band. It was found that the emission of these aggre-
gates showed a blueshift of about 170 nm upon 405 nm
wavelength irradiation, accompanied by enhanced fluores-
cence intensity upon extended UV irradiation (Figure 6d–
e). The time-dependent fluorescent spectra of the nanosph-
eres of 2 with 405 nm UV irradiation are shown in Fig-
ure 6f. This process is very fast: 2.5 min irradiation led to
complete emission shifts from 750 to 580 nm. In addition,
self-assembled samples with other morphologies, such as
nanoslices, also exhibit the same phenomena of blueshifted
and enhanced fluorescence upon extended UV irradiation
(Figure 6b). Spin-coated films without self-assembly did not
show blueshifted emission upon UV light irradiation (Fig-
ure S5).
Figure 4. (a) SEM and (b) TEM images of 2 assembled in CH2Cl2/
hexanes (1:1) at room temperature; (c) SEM and (d) TEM images
of 2 assembled in CH2Cl2/acetone (1:1, v/v) at room temperature.
(e) Proposed mechanism for the supramolecular organization of 2.
As shown in Figure 5, the absorption and emission spec-
tra of the self-assembled nanostructures from CH2Cl2/hex-
ane (v/v, 1:1) were redshifted compared with those from
structures obtained from CH2Cl2, which indicated that the
nanospheres formed in this condition were J-type aggre-
gated (Figure 4e). In the mixed CH2Cl2/acetone solvents,
blueshifted absorption and emission spectra were observed,
Figure 6. (a and b) LSCM of 2 under 405 nm UV irradiation.
(c) Time-dependent intensity plot of the fluorescence emission of 2
(d) before and (e) after UV irradiation for 5 min. (f) Time-depend-
ent emission spectra of self-assembled 2 under UV irradiation (the
numbers 4, 5 and 6 represent the different chosen areas on the
cover glass).
Figure 5. Normalized (a) absorption and (b) emission (excited at
480 nm) spectra of aggregations of compound 2 from CH2Cl2 and
mixed solvents CH2Cl2/acetone and CH2Cl2/hexane.
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Figure 7. Calculated spatial distributions of HOMO and LUMO for 2 at the B3LYP/6-31G(d,p) level on conformations A, B and C,
calculated with Spartan programs.
The conformation of compound 2 varies significantly absorbance of the thiophenes at 380 nm decreased upon
when going from an isolated molecule (in which the single UV irradiation, which supports the conclusion that a con-
bond connecting the perylene bisimide unit and the thio- formational change occurs around the oligothiophene moi-
phene group can rotate freely) to the solid state (in which ety. The thiophene rings in the nonfused trithiophene unit
the rotation is locked by packing effects), thus generating rotate to the less stable conformations B and C, which de-
different chemical environments owing to specific intermo- creases the extent of conjugation of the trithiophene unit
lecular interactions. In the solid state, conformation con- and leads to less ICT (a small decrease was observed for
straints limit the rotation of the perylene bisimide groups the ICT absorption band around 550–700 nm; Figure S6).
due to packing effects. However, the thiophene units can
Solid-state effects can potentially slow down nonradia-
still flip within the cavity provided by the bulky perylene tive decay pathways that involve conformational degrees of
bisimide terminals. The most stable conformation for 2 is freedom, which is a phenomenon known as AIE. The weak
when the three thiophene rings are located on a plane with emission of 2 in solution is attributed to ICT from the tri-
crosswise packing, which is identical to the same part of thiophene unit to the perylene bisimide and to intramolecu-
the most stable thermodynamic conformation A (with the lar rotation of the perylene bisimide rings around the thio-
minimization energy of –6184.1864 a.u) of 2 obtained by phene rings. Strong emission in the solid state would be
the calculations (Figure 7a).[18] The densities in the HOMO expected to result from restriction of intramolecular rota-
orbitals are concentrated on the thiophene ring moiety, tion. Therefore, it is expected that, with obstruction of the
whereas the densities in the LUMO orbitals delocalize on charge transfer from the thiophene units to the perylene
both PDI units, which means that intramolecular charge bisimide, the characteristic AIE phenomena of bulky per-
transfer takes place from the thiophene to the perylene bis- ylene bisimide terminals would be enhanced, that is, the
imide, as evidenced by the shoulder absorption of 2 in the emission at 750 nm would be expected to disappear and the
550–700 nm region. With sufficient energy (excitation at emission at 580 nm should increase.
405 nm, the frequency at which thiophene units absorb), the
thiophene rings in the nonfused trithiophene unit can rotate
to the less stable conformations B and C (with minimized
energy of –6311.7275 a.u and –6209.0661 a.u, respectively),
Conclusions
in which the electron-donating ability of the trithiophene
A thiophene-substituted perylene bisimide has been syn-
unit decreases and the HOMO and LUMO orbital distribu- thesized and used to demonstrate a relatively simple associ-
tions also change (Figure 7b–7c). In contrast to the situa- ated approach to the construction of nano- and micro-
tion with conformation A, the LUMO orbitals of confor- structures with zero and two dimensions. The thiophene-
mations B and C are mainly concentrated on one of the substituted perylene bisimide showed conformation-de-
PDI units, which indicates that conformation A has a pendent hypochromatic shift and fluorescent enhancement
stronger ICT tendency. For the nanosphere film of 2, the behavior in the solid state, which is induced by tuning the
4
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Controllable Supramolecular Architectures
123.1, 122.7, 30.1, 29.5, 24.2 ppm. IR (KBr): ν = 2961, 2925, 2868,
˜
intramolecular charge transfer from the trithiophene unit to
the perylene bisimide through light-induced conformation
changes of the trithiophenes. The mechanism differs from
the fluorescent bleaching of normal solid-state fluorescent
materials, and suggests potentially important applications
in optical devices. This work demonstrates the importance
of controlling molecular conformation in molecular aggre-
gation systems to modulate optical properties.
1706, 1667, 1590, 1457, 1401, 1339, 1248, 1199, 970, 813 cm–1.
HRMS (MALDI-TOF): calcd. for C108H88N4O8NaS3 [M + Na+]
1687.56565; found 1687.56563.
Supporting Information (see footnote on the first page of this arti-
cle): UV/Vis and fluorescence spectra, 1H NMR, 13C NMR and
HR mass (MALDI TOF) spectra for final product 2.
Acknowledgments
This work was supported by the National Nature Science Founda-
tion of China (21031006, 91227113, and 21322301), the NSFC-
DFG joint fund (TRR 61), the National Basic Research 973
Program of China (2011CB932302 and 2012CB932900), and the
“Strategic Priority Research Program” of the Chinese Academy of
Sciences (XDA01020304).
Experimental Section
General Methods: N,NЈ-Bis(2,6-diisopropylphenyl)-1-bromoper-
ylene-3,4:9,10-tetracarboxylic acid diimide and 2,2Ј-([2,2Ј:5Ј,2ЈЈ-
terthiophene]-4,5ЈЈ-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
were synthesized according to the literature.[20] 1H NMR
(400 MHz) spectra were recorded in deuterated solvents with a
Bruker Avance 400 NMR spectrometer. 13C NMR (100 MHz)
spectra were recorded with a Bruker Avance 400 NMR spectrome-
ter. Mass spectra (MALDI-TOF-MS) were determined with a
Bruker Biflex III mass spectrometer. Electronic absorption spectra
were measured with a JASCO V-579 spectrophotometer in a quartz
cell. Fluorescence excitation and emission spectra were recorded
with a Hitachi F-4500 spectrometer at room temperature. Fluores-
cence quantum yields were determined by using the optical dilute
method with N,NЈ-bis(2,6-diisopropylphenyl)perylene-3,4:9,10-tet-
racarboxylic acid diimide (PDI) in CH2Cl2 as reference (Φfl = 1.0).
Cyclic voltammograms (CVs) were recorded with a CHI660D elec-
trochemical workstation at a scan rate of 100 mVs–1, with glassy
carbon electrode as the working electrode, Pt wire as the counter
electrode, and an SCE as the reference electrode. 0.1 m tetrabut-
ylammonium hexafluorophosphate (Bu4NPF6) in dichloromethane
(CH2Cl2; HPLC grade) was employed as the supporting electrolyte.
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Published Online: ᭿
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O42460
/KAP1
Date: 03-07-14 16:15:35
Pages: 7
Controllable Supramolecular Architectures
Solid-State Structures
Light-controlled intramolecular charge
transfer from the trithiophene unit to the
perylene bisimide in the solid state can in-
duce a hypochromatic shift and enhanced
fluorescent emission.
R. Jiang, Z. Xue, Y. Li,* Z. Qin, Y. Li,*
D. Zhu .............................................. 1–7
Controllable Supramolecular Architectures
for Modulating Optical Properties on the
Molecular Aggregation Level
Keywords: Conjugation / Nanostructures /
Nanoparticles / Charge transfer / Solid-
state structures
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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