Three polymorphs of one luminogen: How the molecular packing affects the RTP and AIE properties?

Article abstract of DOI:10.1039/c7tc03656f

Polymorphism of organic molecules has received special attention, since the significantly different photophysical properties can provide important information to build a bridge between the micro- and macro-world. Here, we report three crystalline polymorphs of CzS-CN, which display much different properties of room temperature phosphorescence (RTP) and aggregation-induced emission (AIE). Due to their different molecular packings, the RTP lifetimes change from 266 ms to 41 ms, and then to 32 ms, accompanied by different photoluminescence quantum yields of crystals from 22.6% and 17.8% to 6.9%. Careful analyses of these crystal structures demonstrate that the properties are highly related to the packing mode and molecular configuration, regardless of the same chemical structure, thus disclosing some important clues to understand the structure-packing-property relationship of RTP and AIE performances.

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Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
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Three polymorphs of one luminogen: How the molecular packing
affects the RTP and AIE properties？
Jie Yang,a Zichun Ren,a Bin Chen,b Manman Fang,a Zujin Zhao,b Ben Zhong Tang,b Qian Peng,c and
Zhen Lia,*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Polymorphism of organic molecules has received special attention,
since the significantly different photophysical properties can
provide important information to build a bridge between the
micro- and macro-world. Here, we report three crystalline
polymorphs of CzS-CN, which display much different properties of
room temperature phosphorescence (RTP) and aggregation-
induced emission (AIE). Due to the different molecular packing,
the RTP lifetimes change from 266 ms to 41 ms, then to 32 ms,
accompanying with the different photoluminescence quantum
yields in crystal from 22.6% and 17.8% to 6.9%. Careful analyses
on these crystal structures demonstrate that the properties are
heavily related to the packing mode and molecular configuration,
regardless of the same chemical structure, thus disclosing some
important clues to understand the structure-packing-property
relationship of RTP and AIE performance.
Figure 1 The molecular structure of CzS-CN and the related
photoluminescence (PL) data about RTP and AIE properties
(the αAIE values are the ratio of PL quantum efficiencies in solid
state and solution) for three polymorphs (upper); the
photographs taken at different time, before and after turning-
off the 365 nm UV-irritation under ambient conditions (down).
Organic π-conjugated molecules have attracted increasing
attention for their potential applications in the fields of organic
field-effect transistors (OFET), organic lasers, photovoltaic
cells, stimuli-responses and so on.1 Apart from the electronic
nature of molecular structure, the molecular packing also
shows large impact on the optoelectronic property, as
functional π-conjugated molecules mainly exist in solid state
for practical applications. Thanks to the enthusiasm of
scientists, the investigation on how the molecular packing
affecting related property has become a hot research topic.2
Particularly, polymorphism of organic molecules has received
special attention, since the different molecular packing often
leads to the diverse properties, and the direct comparisons
would be much beneficial to figure out the packing-property
relationship,
then achieve the excellent optoelectronic performance.3 For
example, Bao et al. successfully obtained previously unknown
polymorphs of a small-molecule organic semiconductor with
nearly order-of-magnitude improvement for its field-effect
mobility (1.8 to 11 cm2 V-1 s-1);4 Wang et al. utilized a series of
organic polymorphs for the different organic laser
applicability;5 Seki et al. realized the mechano-responsive
polymorphs with different emission colors (blue to yellow);6
and Hall et al. crystallized the polyaromatic hydrocarbon
coronene in the presence of a magnetic field and obtained a
β−herringbone
structure
instead
of
the
ubiquitous γ−herringbone structure, accompanying with the
extended absorptions from UV to near-IR.7
Recently, organic luminogens with room temperature
phosphorescence (RTP) have attracted great attention for their
full utilization of the excited state energy and long lifetime.8
However, most of the RTP systems contained noble metals,
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(A)
and the alternative metal-free phosphors were seldom
reported, partially due to the lack of reliable guidance and
unclear inherent mechanism.9 In this communication, we
integrated phenthiazine and benzonitrile together to yield a
new RTP luminogen of CzS-CN. Excitedly, through simply slow
solvent evaporation in different initial solutions, three
crystalline polymorphs were cultured including crystal (A),
crystal (B) and crystal (C), which displayed different RTP
lifetimes from 266 ms to 41 ms, then to 32 ms, accompanying
with the different PL quantum yields from 22.6% and 17.8% to
6.9% (Figure 1 and Figure S1). Furthermore, CzS-CN was found
to show typical characteristic of aggregation-induced emission
(AIE, very weak emission in solution, however much enhanced
one in aggregate and solid states). Once being ground, the PL
emission peak could be tuned from 430 to 497 nm, indicating
the highly contrast mechanochromism effect. Careful analyses
of its crystal structures confirmed that the emissive properties
are heavily related to the packing mode and molecular
configuration. To the best of our knowledge, this is the first
time to investigate the RTP and AIE effects with three
polymorphs for the same luminogen. Herein, we present the
synthesis, AIE, RTP and mechanochromism characterizations,
crystal analyses and preliminary theoretical calculations of CzS-
CN in detail, to understand the structure-packing-property
relationship.
(B)
τ
τ
τ
= 226 ms
= 41 ms
= 32 ms
Crystal (A)
Crystal (B)
Crystal (C)
Crystal (A)
Crystal (B)
Crystal (C)
As Prepared Powder
5
10 15 20 25 30 35 40 45 50
0
500
1000
Time (ms)
= 43 ms
As prepared
= 11 ms
= 14 ms
1500
2000
2
θ
(deg)
(C)
τ
τ
τ
(D)
As Prepared
Ground
Fumed
Ground
Fumed
0
200
400
600
800 1000
385
485
585
685
Time (ms)
Wavelength (nm)
Figure 2 The changes of RTP lifetimes in different solid states.
(A) PXRD patterns for CzS-CN in different crystal states and as
prepared powder; (B) Time-resolved PL-decay curves for the
room temperature phosphorescence in different crystal states;
(C) PL spectra for the as prepared, ground and fumed CzS-CN
powder (Insert: the photos for the as prepared, ground and
fumed CzS-CN powder under 365 nm UV-irridation); (D) Time-
resolved PL-decay curves for their room temperature
phosphorescence in different state (as prepared, ground and
fumed) (Insert: the photos of as prepared CzS-CN powder
taking at different times, before and after turning off the 365
nm UV-lamp).
As shown in Scheme S1, CzS-CN could be conveniently
synthesized through one step. Its UV-visible absorption
spectrum was measured in THF solution. There were mainly
two absorption peaks at 256 and 284 nm in deep violet region,
indicating the limited conjugation (Table S1 and Figure S2).
CzS-CN gave a very weak emission at about 529 nm in THF
solution with a PL efficiency as low as 2.1%, mainly caused by
the motions of phenthiazine, cyan groups and phenyl ring
(Figure S3). After large amounts of water (fW > 90), a poor
solution, were added, the emission largely enhanced for the
restricted intermolecular motions upon the formation of
aggregates, demonstrating the AIE characteristic of CzS-CN.10
Three single crystals of CzS-CN were obtained through slow
solvent evaporation, with their structural data summarized in
Table S2. The powder X-ray diffraction (PXRD) measurement
was carried out for the three polymorphs and powders. As
shown in Figure 2A, these three crystals presented different
PXRD peaks, indicating their different molecular packing. As for
the as prepared powder, its PXRD peaks were similar to those
of crystal (B), suggesting it mainly existed in the form of crystal
(B). On the other hand, their PL spectra, including fluorescence
and phosphorescence, and the corresponding lifetimes at
room temperature as well as at 77K were also much different
from each other (Figure S4-S8). Particularly, the RTP lifetimes
for the three polymorphs could change from 266 ms to 41 ms,
then to 32 ms (Figure 2B), accompanying with the different
photoluminescence quantum yields from 22.6% and 17.8% to
6.9%.
mechanical stimulation (Figure 2C). The high contrast
mechanochromism effect as large as 67 nm should be mainly
originated from the transition from crystal to amorphous state
as well as the structural co-planation.11 In the meantime, its
RTP effect also could be weakened by grinding, with RTP
lifetimes shortening from 43 ms for the as-prepared powder to
11 ms in the ground state (Figure 2D). Thus, the different PL
behaviors in different states could further prove the significant
influence of molecular packing on the emissive property.
To explore the underlying mechanism of the emissive
property of CzS-CN, the crystal analyses of these three
polymorphs were further performed. First, the molecular
configurations were taken into consideration for the possible
influence on their emissive property, coupled with the
preliminary theoretic calculations. As shown in Figure 3, the
molecular configurations for CzS-CN in the three crystals were
different from each other. In crystal (A), the molecule showed
a highly twisted conformation with the torsion angel for
phenothiazine moiety about 48o while about 117o between
phenothiazine and benzonitrile groups. As for crystal (B), two
minor different configurations, crystal (B1) and crystal (B2),
were observed, which showed the similar torsion angels of
116o between phenothiazine and benzonitrile groups as crystal
(A), but less twisted phenothiazine moieties with torsion
angels of 42-43o. Differently, crystal (C) showed a more planar
configuration in the long axis direction, with the torsion angels
Besides, CzS-CN showed much different emissive property in
different powder states―as prepared, ground and fumed
powders (Figure S9-S10). Particularly, its emissive peaks could
change from 430 nm to 497 nm, just upon the simply
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LUMOs all spread on the whole molecules, and the large
overlap between
Figure
3 (A) The energy level diagram and molecular
Figure 4 (A) Entire (left) and local (right) packing modes of the
crystal (A) for CzS-CN; (B) Entire (left) and local (right) packing
modes of the crystal (B) for CzS-CN; (C) Entire (left) and local
(right) packing modes of the crystal (C) for CzS-CN. (The local
packing pictures were selected from the parts in cycles of
corresponding entire ones. In entire packing, the strong π-π
interactions were labeled by pink color, weak π-π interactions
were labeled by rose color and intermolecular hydrogen bonds
less than 3.0 Å were linked, while in local packing, the
intermolecular interactions were labelled and listed).
configuration for crystal (A); (B) The energy level diagram and
molecular configuration for crystal (C); (C) The energy level
diagram and molecular configuration for crystal (B1); (D) The
energy level diagram and molecular configuration for crystal
(B2).
between phenothiazine and benzonitrile groups about 127o,
although it was 56o in the phenothiazine moiety. Thus, the
different molecular configurations in crystals could surely
make some influences on their different emissive properties.
In order to study the influence of the molecular
configurations on their RTP effect, TD-DFT calculations on
energy level and related excited state transition configurations
for singlet and triplet states were carried out by b3lyp/6-31g*
(Figure 3), based on the single crystals. The notations of H and
L referred to the highest occupied molecular orbital (HOMO)
and the lowest unoccupied molecular orbital (LUMO), while
orange arrows referred to the possible ISC channels. The major
ISC channels were mainly determined based on two elements-
Tn gave a small energy gap (< 0.3 eV) with S1, and contained
the same transition orbital compositions as S1 state.8a When
the energy of Tn was similar or lower than that of S1, the latter
element was considered to be more important. The
determination of minor ISC channels was vice versa. For crystal
(A), there were three major and one minor ISC channels, while
those of crystal (C) were much less with only one major and
one minor, owing to the big changes of the molecular
configuration. Crystal (B1) and (B2) showed the same ISC
transitions of two major and four minor ISC channels, for their
similar molecular configurations. Thus, as demonstrated in the
calculation results, more efficient ISC transitions of crystal (A)
and (B) rather than those of crystal (C), could be in well
accordance to their RTP properties, that is, crystal A and B
gave much stronger RTP emissions than crystal (C) after
turning off the UV-irritation.
HOMOs and LUMOs could surely contribute much to their PL
efficiencies. Among them, crystal (C) gave the highest
oscillator strength (f) for the more planar configuration in the
long axis direction, up to 0.21. However, crystal (A), (B1) and
(B2) showed similar oscillator strength (f), from 0.12-0.13, for
their minor different molecular configurations. Based on these
calculations, crystal (C) should give the more efficient emission
than others. But actually it was not, indicating that the
molecular configuration could gave some influence on the
emissive property to some extent, but it was not the sole
determining factor.
Generally, the main distinctions for polymorphs are the
packing mode and molecular configuration. Thus, the
molecular packing mode should be considered seriously. As
shown in Figure 4, all of them showed different packing mode,
accompanying with the diverse intermolecular interactions. In
order to simplify the packing analyses and make a clear
description of their distinctions, coupled units of two
molecules with strong intermolecular interactions were
selected and listed. In crystal (A), there were mainly two kinds
of coupled units―coupled I and coupled II. In coupled I, two
phenothiazine groups interacted with each other through π-π
(3.55 Å), C-H…π (2.76-3.49 Å) and C-H…N (3.72 Å) bonds, while
just hydrogen bonds of C-H…π (2.57 Å) and C-H…N (3.01-3.90
Å) were observed in coupled II. The strong intermolecular
interactions would restrict the intermolecular motions
effectively and lead to the reduced non-radiative transition,
which could surely contribute much to the long RTP lifetime
(266 ms), as well as its high PL quantum efficiency (22.6%).
The theoretic analyses on S0→S1 transitions were carried out
to explore the possible influence of molecular configurations
on the different PL quantum yields.[12] As shown in Figure S11
and Table S3, the electron coefficients in the HOMOs and
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However, the intermolecular interactions in crystal (B) were moments for isolated molecules in the three polymorphs, and
much weaker. Because of the existence of two different found that all of them were parallel to the long axis (Figure
molecular configurations, three kinds of coupled units were S14). However, significant different transition dipole moments
observed. In coupled I and II (Figure 4B), two phenothiazine would occur in the different packing modes (Figure S15).14 In
groups interacted with each other mainly through weak C-H…π crystal (C), the coupled II presented a parallel stacking mode in
bonds (3.54-3.70 Å), while multiple hydrogen bonds of C-H…π the long axis, thus the lowest excited state corresponded to
(2.95-3.11 Å) and C-H…N (3.45-3.92 Å) were found in coupled the destructive combination of the transition dipole moment
III. Thus, the weaker intermolecular interactions in crystal (B) for the individual molecule, which was optically forbidden and
would result in the short RTP lifetime (41 ms) and a relatively would result in the low PL efficiency (6.9%). As for crystal (A)
lower PL quantum efficiency (17.8%) in comparison with and crystal (B), the more twisted configurations in the long axis
crystal (A). As for crystal (C) (Figure 4C), although multiple π-π made them tend to form X-type packing modes (couple II in
(3.84 Å), C-H…π (3.03-3.52 Å) and C-H…N (3.54 Å) bonds in crystal (A) with cross angle about 67o and coupled III in crystal
coupled I could restrict the non-radiative motions effectively, (B) with cross angle about 62o), in which the energy splitting
the formed H-type packing mode in coupled II, originated from between the lowest two excited states of the coupled units
the more planar configuration in the long axis direction, would would be much reduced, and a progressive transfer from the
result in the much lower PL efficiency (6.9%).12 In crystal (A) second excited state to the lowest excited state could occur.
and crystal (B), the more twisted configurations in the long axis This level distribution promoted a finite transition dipole
made them tend to form X-type packing modes (couple II in moment between the ground state and the lowest excited
crystal (A) and coupled III in crystal (B)), which could restrict state, thus led to the much higher PL efficiencies―22.6% for
the energy lose. Thus, their different packing modes, derived crystal (A) and 17.8% for crystal (B).
from the different molecular configurations, should be mainly
As revealed by our experimental results, two main kinds of
responsible for their diverse AIE effects. As for the short RTP emissive properties, RTP and AIE ones, are heavily related to
lifetime (32 ms) of crystal (C), it was the molecular the molecular packing, including the molecular configuration
configuration, rather than the packing mode, play the more and packing mode, in addition to the chemical structure.
significant role, for the less efficient ISC transition in that Actually, this viewpoint is applicable to other kinds of emissive
configuration.
property, such as PL emissive colors, mechanoluminescence
To get a deep insight into how the packing mode affecting (ML) and so on (Figure S16-S20). For example, Chi et al.
RTP process, the calculation on the energy levels were carried identified that the different dipole moments, derived from the
out on the coupled units picked from the single-crystal different molecular configurations in two polymorphs,
structures. Particularly, the energy gaps between S1 and T1 determined whether there was the ML effect or not.15 Also, we
states were calculated for its significant role in the RTP process proved that the packing mode with stronger intermolecular
(Table S4, Figure S12).13 As shown in Figure S13, the energy interactions in polymorphs played significant influence on the
gaps between S1 and T1 state in coupled units would decrease ML property in our previous work.16 As for the PL emission,
in comparison with those of isolated molecules, which could Dong et al. got two kinds of crystals with blue and green
lead to the reduced energy lose in the process of internal emissions, and they ascribed it to their different distorted
conversion at excited triplet states, thus contribute much to degrees in molecular configurations.17 Furthermore, Wang et
the RTP effect. And, the coupled units with stronger al. could alter the PL emissions from yellow to red through
intermolecular interactions tended to achieve smaller energy simple heating, during which, the particular packing mode
gaps between S1 and T1 states for the strong electron coupling have changed from non-excimer to excimer.[18] Besides these
effect. For the coupled I and II in crystal (A), they showed the beautiful works, really scarce ones have concerned on
smallest energy gaps, Δ(S1-T1), ranging from 0.64 to 0.74 eV, polymorphs to explore the internal mechanisms of RTP and AIE
because of the strong intermolecular interactions. On the effects. Particularly, the study on organic persistent RTP has
contrary, the coupled units in crystal (B), with relatively weak been a new research area, and more thorough mechanisms
intermolecular interaction, gave the larger energy gaps, Δ(S1- are waiting for being revealed, and more efficient RTP
T1), ranging from 0.81 to 0.91 eV. Thus, the smaller energy luminogens are needed to be developed.
gaps between S1 and T1 states in crystal (A) could surely
In summary, we have synthesized a new persistent RTP
contribute much to its long RTP lifetimes of 266 ms rather than luminogn of CzS-CN. Furthermore, it was found to show
that (41 ms) of crystal (B). As for crystal (C), although the interesting AIE and highly contrast mechanochromism effects.
energy gaps in coupled units were moderate (from 0.80 to Particularly, three kinds of crystalline polymorphs for CzS-CN
0.86 eV), the inefficient ISC transitions, originating from the were cultured, in which the RTP lifetimes changed from 266
unique molecular configuration, have produced great ms to 41 ms, then to 32 ms, accompanying with the different
limitations on its RTP effect. Thus different molecular packing, photoluminescence quantum yields from 22.6% and 17.8% to
including molecular configuration and packing mode, should 6.9%. A careful analyses on these crystal structures, coupled
both be heavily related to the RTP effect.
with theoretical calculations, demonstrated that the emissive
As for the changed PL efficiencies in polymorphs, we tried to properties are heavily related to the molecular packing,
explore it through the transition dipoles in different packing including molecular configuration and packing mode, even for
modes. First, we calculated the directions of transition dipole the same compound. Thus, the information gained from this
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Sakamoto, N. Tanaka, J. Seino, H. Nakai, T. Fukushima, J. Am. Chem.
Soc., 2017, 139, 2728-2733; (f) J. Yang, Z. Ren, Z. Xie, Y. Liu, C. Wang,
Y. Xie, Q. Peng, B. Xu, W. Tian, F. Zhang, Z. Chi, Q. Li, Z. Li, Angew.
Chem., 2017, 129, 898-902.
[9] (a) S. Xu, R. Chen, C. Zheng, W. Huang, Adv. Mater., 2016, 28,
9920-9940; (b) S. Hirata, Adv. Optical Mater., 2017, 1700116; (c) M.
Baroncini, G. Bergamini, P. Ceroni, Chem. Commun., 2017, 53, 2081-
2093; (d) S. Mukherjee, P. Thilagar, Chem. Commun., 2015, 51,
10988-11003.
work could help us to make a deep understanding of structure-
packing-property relationship and provide some guidance in
the design of other RTP and AIE luminogens. In addition,
molecular packing should also be considered seriously for
other photophysical process in condensed state. Only with it, a
deep and thorough understanding could be obtained.
Conflicts of interest
[10] J. Mei, N. Leung, R. Kwok, J. Lam, B. Tang, Chem. Rev., 2015,
115, 11718-11940.
There are no conflicts to declare.
[11] C. Wang, Z. Li, Mater. Chem. Front., 2017, DOI:
10.1039/C7QM00201G.
[12] Q. Qi, J. Qian, X. Tan, J. Zhang, L. Wang, B. Xu, B. Zou, W. Tian,
Adv. Funct. Mater., 2015, 25, 4005-4010.
ACKNOWLEDGMENT
We are grateful to the National Science Foundation of China
(no. 21325416, 51573140) and National Fundamental Key
Research Program (2013CB834701) for financial support.
[13] Y. Gong, L. Zhao, Q. Peng, D. Fan, W. Yuan, Y. Zhan, B. Tang,
Chem. Sci., 2015, 6, 4438-4444.
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Journal of Materials Chemistry C
Page 6 of 6
View Article Online
DOI: 10.1039/C7TC03656F
TOC
Three crystalline polymorphs of CzS-CN, which display much different properties of room
temperature phosphorescence (RTP) and aggregation-induced emission (AIE). Careful analyses on
these crystal structures demonstrate that the properties are heavily related to the packing mode
and molecular configuration, regardless of the same chemical structure.