Molecular Engineering through Control of Structural Deformation for Highly Efficient Ultralong Organic Phosphorescence

Article abstract of DOI:10.1002/anie.202011830

It is an enormous challenge to achieve highly efficient organic room-temperature phosphorescence (RTP) with a long lifetime. We demonstrate that, by bridging the carbazole and halogenated phenyl ring with a methylene linker, RTP phosphors CzBX (X=Cl, Br) present high phosphorescence efficiency (Φ_Ph). A Φ_Ph up to 38 % was obtained for CzBBr with a lifetime of 220 ms, which is much higher than that of compounds CzPX (X=Cl, Br) with a C?N bond as a linker (Φ_Ph<1 %). Single-crystal analysis and theoretical calculations revealed that, in the crystal phase, intermolecular π-Br interactions accelerate the intersystem crossing process, while tetrahedron-like structures induced by sp³ methylene linkers restrain the nonradiative decay channel, leading to the high phosphorescence efficiency in CzBBr. This research paves a new road toward highly efficient and long-lived RTP materials with potential applications in anti-counterfeiting or data encryption.

Full text of DOI:10.1002/anie.202011830

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Accepted Article
Title: Molecular Engineering via Controlling Structural Deformation for
Highly Efficient Ultralong Organic Phosphorescence
Authors: Zhongfu An, Zheng Yin, Mingxing Gu, Huili Ma, Xueyan Jiang,
Jiahuan Zhi, Yafei Wang, Huifang Yang, and Weiguo Zhu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202011830
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10.1002/anie.202011830
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Molecular Engineering via Controlling Structural Deformation for
Highly Efficient Ultralong Organic Phosphorescence
Zheng Yin[a,c]+, Mingxing Gu[b]+, Huili Ma[b], Xueyan Jiang[b], Jiahuan Zhi[b], Yafei Wang*[a], Huifang Yang[a],
Weiguo Zhu*[a,c], Zhongfu An*[b]
Abstract: It is an enormous challenge to achieve the highly efficient
organic room-temperature phosphorescence (RTP) with long lifetime.
Here we demonstrated that by bridging the carbazole and
halogenated phenyl ring with methylene linker, a type of RTP
phosphors CzBX (X = Cl, Br) shows high phosphorescence efficiency
(ФPh), up to 38% for CzBBr with a lifetime of 220 ms, which is much
higher than that of compounds CzPX (X = Cl, Br) with C-N bond as a
linker (ФPh < 1%). Single crystal analysis and theoretical calculations
revealed that, in the crystal phase, the intermolecular π-Br interaction
accelerates the intersystem crossing process, while tetrahedron-like
structure induced by sp3 methylene linker restrains the nonradiative
decay channel, leading to the high phosphorescence efficiency in
CzBBr. This research not only paves a new road for achieving highly
efficient and long-lived RTP materials but also expands the
applications in anti-counterfeiting or data encryption.
organic RTP molecules with high phosphorescence efficiency
(ФPh > 20%) were seldom reported.[9] On the other hand, heavy
atoms, like bromine, can largely promote phosphorescence
efficiency but shorten phosphorescence lifetime, thus it is hard to
trigger long-lived RTP.[3e-g,10] Therefore, how to achieve organic
RTP with both high efficiency and ultralong lifetime is an
extremely intriguing topic to explore.
Room temperature phosphorescence (RTP) materials have
been pursued by academics owing to their full utilization of excited
state energy and long lifetimes, which show potential applications
in displays, encryption, anti-counterfeiting, sensors and
bioimaging.[1] However, it is an enormous challenge to realize
efficient RTP in pure organic molecules due to the inefficient
intersystem crossing (ISC) caused by weak spin-orbit coupling
(SOC) and the fast deactivation pathways of triplet excitons.[2]
Recently, numerous strategies have been proposed to overcome
this issue. The common way to promote ISC process is
incorporating the n-electron groups (e.g, aldehyde and carbonyl)
into π-conjugated organic molecules.[3] These compounds have
donor-acceptor skeleton featuring with strong electronic coupling,
which are inclined to forming distinct structural deformation in
excited-state transition process, leading to limited suppression of
molecular motions even restrained by rigid environments, such as
polymer aggregation,[4] host-guest systems,[5] self-assembly,[6]
crystallization,[7] H-aggregation,[8] etc. Consequently, long-lived
Figure 1. a) The schematic illustration of design concept. b) Molecular
structures of CzPX and CzBX (X=Cl, Br).
To address the above issue, we proposed to introduce
methylene linker into the donor-acceptor RTP molecules based
on two rationales: the sp3 methylene 1) makes tetrahedron-like
molecular geometry, favoring formation of strong intermolecular
interaction in crystal[11]; 2) breaks the electron delocalization
between donor and acceptor units, hampering the structural
deformation in excited-state transition. Both features will suppress
the non-radiative decay pathways in the solid state. Besides,
halogennated acceptor could form intermolecular π -halogen
interation in crystal, which only accelerates ISC channel, but not
shortens RTP lifetime.[12]
[a] Z. Yin, Prof. Y. Wang, H. Yang, Prof. W. Zhu
National Experimental Demonstration Center for Materials Science and
Engineering, Jiangsu Key Laboratory of Environmentally Friendly
Polymeric Materials, Jiangsu Collaborative Innovation Center of
Photovoltaic Science and Engineering, Jiangsu Engineering Laboratory
of Light-Electricity-Heat Energy-Converting Materials and Applications,
School of Materials Science & Engineering, Changzhou University,
Changzhou 213164, China
E-mail: qiji830404@hotmail.com; zhuwg18@126.com
[b] M. Gu, Dr. H. Ma, X. Jiang, J. Zhi, Prof. Z. An
Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced
Materials (IAM) Nanjing Tech University (NanjingTech), 30 South Puzhu
Road, Nanjing 211816, China.
E-mail: iamzfan@njtech.edu.cn
[c] Z. Yin, Prof. W. Zhu
College of Chemistry, Xiangtan University, Xiangtan 411105, China
[+] These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of the
document.
With these in mind, we designed and synthesized CzBX (X =
Cl, Br) compounds (Figure 1), i.e., the sp3 methylene linker was
used to bridge carbazole and halogenated phenyl ring. As
expected, CzBX show a huge promotion of RTP efficiency,
compared to the donor-acceptor molecules CzPX (X = Cl, Br,
Figure 1) with low RTP efficiency. Intriguingly, CzBBr crystal
exhibited a high phosphorescence efficiency (ФPh) of 37.96%,
along with a long-lived lifetime of 220.24 ms. Experiments and
theoretical simulations demonstrated that this improvement on
RTP can be ascribed to the largely restricted nonradiative decay
and enhanced ISC channel by both methylene linker and π-
halogen interaction in crystal, respectively. Given the high
efficiency and ultralong lifetime of RTP, these compounds were
finely applied in multiple data encryption technique by utilizing the
time resolution technique.
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Figure 2. Photophysical properties of compounds CzPX and CzBX in crystals under ambient conditions. a) Normalized steady-state photoluminescence (blue line)
and ultralong phosphorescence (red line) spectra of CzPX and CzBX crystals. Insets: the photographs of CzPX and CzBX crystals under 365 nm UV light on (left)
and off (right). b) Lifetime decay profiles of the phosphorescence emission peaks measured under ambient conditions. c) CIE 1931 coordinates of steady-state
photoluminescence of CzBBr crystal excited by 370 nm. d) Excitation-phosphorescence emission mapping of CzBBr crystal. e) Bar charts of phosphorescence
quantum yields of CzPX and CzBX crystals.
little influence on the T1 states. Whereas the phosphoresce ratios
In this work, a series of aromatic amide derivatives with halogen
in CzBX molecules are similar to CzPCl, it speculated that the
substituents, namely, 9-(4-chlorophenyl)-9H-carbazole(CzPCl),
methylene linker may weaken the impact of heavy atom effect,
9-(4-bromophenyl)-9H-carbazole (CzPBr), 9-(4-chlorobenzyl)-
providing a possibility to achieve long-lived RTP in halogenated
9H-carbazole (CzBCl) and 9-(4-bromobenzyl)-9H-carbazole
organic materials.
(CzBBr), were facilely prepared through one-step nucleophilic
substitution reaction (Scheme S2). All target compounds were
thoroughly characterized by 1H and 13C NMR spectroscopy
(Figure S1-S8), elemental analyses and X-ray single-crystal
diffraction. HPLC was carried out to further confirm the purity
(Figure S9-S12).
In crystals, all compounds exhibited bright blue or bluish white
emissions upon irradiated by a 365 nm ultraviolet (UV) lamp. As
shown in Figure 2a, CzPX and CzBX crystals showed a strong
fluorescence emission ranging from 350 to 450 nm with a short
lifetime of ns-scale (Figure S16, Table S2). After removing the
excitation light source, yellowish afterglow was observed by the
naked eye, lasting for several seconds (Video SV1-SV4). With a
delay time of 8 ms, CzPBr displayed a maximal RTP peak around
524 nm with a lifetime of 299.42 ms, along with a shoulder peak
at 560 nm. While CzPCl, CzBCl and CzBBr showed a red-shifted
RTP bands at 550 nm with lifetimes of 224.07, 777.37 and 220.24
ms, respectively, accompanied by shoulders at 600 nm (Figure
2a, 2b). On the other hand, very weak emissions from the region
of 400-520 nm are observed for these compounds, which could
be ascribed to the triplet-triplet annihilation.[10e] Excitation-
phosphorescence emission mappings demonstrated that CzBX
and CzPX crystals all remained their RTP emission positions
when the excitation wavelength changed from 250 to 420 nm
(Figure 2d, Figure S15). Impressively, CzBBr has an intense RTP,
which can be comparable to its fluorescence emission, resulting
in a distinct white luminescence with a CIE (Commission
International de I'Eclairage) of (0.34, 0.30) under UV irradiation
(Figure 2c). This is different to blue luminescence in other three
compounds owing to the faint RTP emission. Unsurprisingly,
CzBBr exhibits a high RTP efficiency, up to 37.96%, and this
Firstly, the photophysical properties of these compounds both
in solution and crystal were systematically explored by absorption
spectra, steady-state photoluminescence (PL) spectra and time-
resolved emission spectra (TRES). The absorption bands of
compound CzPX in 2-methyltetrahydrofuran (2-MeTHF) solution
are located at ca. 240, 291, 325 and 338 nm, and those for CzBX
red-shifted to 240, 292, 328 and 341 nm (Figure S13a and Table
S1) under ambient condition. While these four compounds show
similar steady-state PL emission peaks at 350 and 365 nm in 2-
MeTHF solution, but display a small difference to the structured
emission profiles (Figure S13b and Table S1), which can be
attributed to the variation of singlet excited states caused by
methylene linker. At 77 K, the fluorescent spectra present dual
emissions in the solution, in which the high-energy regions are
attributed to the fluorescence, while the low-energy region is
regarded as the phosphorescence. It is worthy noting that the
CzPBr has the largest phosphoresce ratio, which can be ascribed
to the efficient intramolecular heavy-atom effect. One the other
hand, these compounds show almost identical phosphorescence
profile (Figure S14), indicating the methylene and halogens have
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Figure 3. The intermolecular interactions around one molecule in CzPX (a, b) and CzBX (c, d). e) The calculated free volume region in the single crystal cells of
CzPX and CzBX. Intermolecular heavy-atom interactions of CzPBr (f) and CzBBr (g).
CzPBr. On the other hand, the molecules in a crystal lattice
value is less than 1% for CzPBr, CzBCl and CzPCl (Figure 2e,
usually occupy most of the space of a unit cell. However, there
Table S3). To the best of our knowledge, this is one of the highest
are plenty of unoccupied spaces, i.e., the free volume, which can
RTP efficiency among the reported single component organic
afford the molecular motions with nonradiative decay process.[13]
RTP molecules with long afterglow (Figure S18). Notably, the
As shown in Figure 3e, we calculated the free volume distribution
phosphorescence is highly sensitive to oxygen. Therefore, the
of the compounds CzPX and CzBX. Intriguingly, by introducing
control experiments on the steady-state photoluminescence
the methylene linker, the fractional free volumes are decreased
spectra of model CzBCl phosphor were conducted in vacuum and
from CzPX (~7%) to CzBX (~4%) (Figure S21). The tendency is
oxygen (Figure S19). We found that no phosphorescence band
consistent with the reduced nonradiative decay rates of T1 states
appeared in vacuum, indicating the ambient conditions have little
(Table S4), which can be ascribed to the restricted twisted
influence on the phosphorescence efficiency. Because the
vibrations in the low-frequency regions (Figure S22). These
phosphorescence can be largely preserved by the rigid molecular
results showed that CzBX crystals afford more rigid environment
stacking in crystal state.
with aid of the methylene linker, which can prevent molecular
motions and stabilize triplet excitons, facilitating the generation of
efficient RTP. More importantly, Figure 3f, 3g displayed that the
Single crystal analysis was then carried out to elucidate the
intrinsic RTP mechanism. As shown in Figure 3 and S20, CzBX
adopts tetrahedron-like conformations with amounts of
intermolecular interactions, such as C-H···π (2.854, 2.866, 2.891,
2.893 Å) and C-H···H-C (2.388 Å) in CzBBr crystals, whereas
CzPX possesses less intermolecular interactions, such as C-
H···Br-C (2.986 Å) and edge to face π···π (3.338 Å) contacts in
angle between bromine atom and carbazole plane (αBr π=138.16°,
⋯
138.26°) in CzBBr is largely smaller than that in CzPBr
(αBr π=177.86°). It speculated that CzBBr has efficient C-Br⋯π
⋯
interaction, which can promote ISC process significantly, leading
to high RTP efficiency (37.96%) in CzBBr.[11] Similar halogen-π
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Figure 4. Electronic structure natures for CzPBr and CzBBr. a) Natural transition orbitals (NTOs) of S1 states. b) The dihedral angles tween carbazole and phenyl
ring (φ) of S0, S1 and T1 states. c) Calculated energy diagram, oscillator strength (f) and spin-orbit coupling (SOC) matrix elements (ξ) . (d) Proposed RTP
mechanism.
1.416 to 0.216 cm-1, implying that the methylene linker reduces
interaction was also found in CzBCl (Figure 3c), but there existed
the internal heavy atom effect. It results in a limited acceleration
of ISC channel for CzBBr. We then turn into probe the
intermolecular π-halogen interaction. A model system of CzPBr
low RTP efficiency (0.57%), which might be attributed to the
negligible heavy atom effect due to the light Cl atom.
surrounding a BrH moleclue, named as CzPBr-Ext, was firstly
built based on molecular packing in single crystal. Impressively,
the SOC value of S1→T4 is increased from 0.331 cm-1 in CzPBr
to 2.060 cm-1 in CzPBr-Ext, along with the unchanged ∆EST.
Whereas this π-halogen interaction cannot increased the SOC
values in CzBCl (Figure S25). Thus, the π-halogen interaction can
be responsible for the large ISC rate (3.80×107 s-1) in CzBBr,
which is larger two orders of magnitude than that in other three
compounds (Table S4). Subsequently, this large SOC also makes
a huge increase of oscillator strength (1.57×10-6) of T1→S0 for
CzBBr-Ext, in comparison to 5.67×10-8 for CzPBr and for 1.38
×10-7 for CzBBr. Such tendency can be reponsible for the
decreased radiative decay rate of T1→S0 from CzBBr (1.73 s-1) to
CzPBr (0.70×10-2 s-1) (Table S3), in combination with the almost
unchanged SOC values of ξ(T1,S0). Whereas the nonradiative
decay rate of T1→S0 has a small change for these compounds,
owing to the almost unchanged T1 states with a local transition on
carbazole units (Figure S23). Therefore, the increased ISC and
radiative decay process make the high RTP efficiency in CzBBr.
To gain deep insight into the high RTP efficiency in CzBBr caused
by methylene linker, we evaluated the electronic structure natures
of CzPBr and CzBBr at the level of (TD)B3LYP/cc-pVDZ,
including excitation energy, natural transition orbitals (NTOs) and
spin-orbit coupling (SOC) matrix elements (ξ), as well as
reorganization energy (λ) shown in Figure 4. When going from
CzPBr to CzBBr, the methylene linker makes the singlet excited
state S1 changed from delocalization transition on the whole
molecule to local carbazole transition. This means that the
structure deformation in the excited states decay process of
CzPBr is much larger than that of CzBBr, which was further
verified by the fact that the dihedral angle (φ) between carbazole
and phenyl ring is changed from 38.77° in S1 to 42.06° in S0 states
for CzPBr, and such variation is hugely reduced from 56.92° in S1
to 56.19° in S0 states for CzBBr. Consequently, the λ of S1 state
is decreased from 0.162 eV in CzPBr to 0.104 eV in CzBX (Table
S6), which is responsible for the sharply decreased nonradiative
decay rates of S1 state from 8.05 × 108 s-1 in CzPBr to 3.14×107
s-1 in CzBBr (Table S4), resulting in a hugely increase of PL
quantum yields from 6.60% in CzPBr to 68.60% in CzBBr (Table
S3), combining with a little increased radiative decay rates due to
the small change of oscillator strength (Figure 4c, Table S3). On
the other hand, from CzPBr to CzBBr, the energy gaps (∆EST) of
S1→T4 and S1→T3 are reduced from 0.25 eV, 0.50 eV to 0.003
eV, 0.26 eV, respectively, which facilitates the promotion of ISC
channel. However, the SOC value of S1→T3 is decreased from
Taken these results together, we proposed that the fast
nonradiative decay rate of S1 states was responsible for the low
PL efficiency in CzPBr (Figure 4d), owing to the large structural
deformation. When the methylene liner breaks the π-conjugation,
the S1 state in CzBBr becomes to a local carbazole transition,
which largely reduced the nonradiative decay process, while the
intermolecular π-halogen interaction hugely promotes the ISC of
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S1→Tn and radiative decay rate of T1→S0 (Figure 4e). However,
it has little impact on the SOC of T1→S0. Consequently, both high
RTP efficiency and long-lived RTP lifetime are achieved in CzBBr.
naked eyes or a camera with low sensitivity and short exposure
time. Only under the camera with high sensitivity and long
exposure time, the hidden information can be found. Within 0 to
0.5 s after witching off the UV-lamp, eight stars fabricated by
CzPBr can be observed (Info. 1), while within 2 to 3.5 s after
witching off the UV-lamp, the crescent pattern fabricated by
CzBCl can be observed (Info. 3).
In summary, a series of efficient pure organic phosphors,
named CzPX and CzBX (X = Cl, Br) was developed bearing
carbazole and halogen-substituent phenyl moieties. These
molecules showed long-lived RTP lifetimes in the range of 200 to
900 ms. We found that compounds CzBX with tetrahedron-like
geometries could largely suppress the molecular motions in
excited stated decay process after introducing sp3 methylene
linkers into the CzPX molecules. Moreover, the intermolecular π-
halogen interaction has a large increase to the ISC and radiative
decay channel, but it has a tiny influence on the nonradiation
transition of T1→S0. Whereas it is invalid to CzBCl due to the light
Cl atom. Consequently, CzBBr presented a long RTP lifetime and
high RTP efficiency, up to 38%. This research paves a new road
for achieving highly efficient pure organic phosphors.
Given the unique RTP characteristic with ultralong RTP lifetime,
these compounds can be finely applied in multiple anti-
counterfeiting or data encryption technique by utilizing the time
resolution technique. In Figure 5a, the fitted lines of luminescence
decay process of CzBBr, CzBCl and CzPBr are demonstrated in
log 10 and linear modes. With the longest lifetime, the
phosphorescence of CzBCl can last over 7 s. Moreover, with the
highest phosphorescence efficiency, CzBBr can show the highest
brightness in the same conditions, but its afterglow can only last
for about 3 s for its shorter lifetime. With shorter lifetime and lower
efficiency, CzPBr can hardly be observed. When they were
fabricated in one pattern at the same time, different information
can be observed under the different conditions. As illustrated in
Figure 5d and 5e, under the irradiation of a 365 nm UV-lamp, the
pattern only shows a white circular pattern fabricated by CzBBr
(Info. 2). While the UV-lamp was switched off, the pattern can still
keep an orange circular pattern (Info. 2) under the observation of
Figure 5. The application of data encryption based on CzBBr, CzBCl and CzPBr. a) The fitted lines of luminescence decay process with log 10 and linear modes,
respectively. b) The structure of pattern for security application using CzBBr, CzBCl and CzPBr. c) Three encrypted information patterns from the device. d)
Photographs of the pattern under visible and UV light, respectively. e) Photographs of the pattern taken after tuning off the UV light with two different shooting
modes under ambient conditions.
5181102002 and 21973043), Natural Science Foundation of
Hunan Province (2017JJ2245, P201903), and the Talent project
Acknowledgements
of Jiangsu Specially-Appointed Professor, Open Project for the
National Key Laboratory of Luminescent Materials and Devices
Thanks to the financial supports from the National Natural
(2017-skllmd-12), Brand Specialty & Preponderant Discipline
Science Foundation of China (51773021, U1663229, 51473140,
Construction Projects of Jiangsu Higher Education Institutions.
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We are grateful to the High Performance Computing Center in
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resources.
Keywords: crystal engineering • sp3 methylene linker • organic
room-temperature phosphorescence • intermolecular
interactions
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10.1002/anie.202011830
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
Zheng Yin+, Mingxing Gu+, Huili Ma,
Xueyan Jiang, Jiahuan Zhi, Yafei
Wang*,Huifang Yang, Weiguo Zhu*,
Zhongfu An*
Page NO. – Page NO.
Molecular Engineering via Controlling Structural
Deformation for Highly Efficient Ultralong Organic
Phosphorescence
Through controlling the molecular motions by appending a sp3 methylene fragment and utilization of intermolecular Br-π interaction,
compound CzBBr shows excellent RTP with an ultrahigh ФPh up to 38% and an ultralong lifetime of 220 ms.
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