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DOI: 10.1039/D0CC02730H

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Tunable room temperature phosphorescence and energy transfer

in ratiometric cocrystals
Received 00th January 20xx,
Bo Zhou1, Qihang Zhao1, Longchang Tang1 and Dongpeng Yan*1.2
Accepted 00th January 20xx

ChemComm Accepted Manuscript

DOI: 10.1039/x0xx00000x

Two corystals (BTA-ME-1 and BTA-ME-2) assembled with same photonic/electronic performances by designing and controlling
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building blocks but different ratios exhibit alternative stacking the crystal stacking modes and noncovalent intermolecular
mode, relative orientation and aggregation state, leading to color- interactions.12,13 It is reported that fluorescence can be also
tunable green and yellow room temperature phosphorescence modulated in cocrystal systems by altering different components
(RTP) and different intermolecular energy transfer efficency, (co-formers) and different crystal structures;14-16 however,
respectively. Based on the time-resolved afterglow properties of studies on RTP cocrystals are still relative limited to date. In
the RTP emission, BTA-ME-2 is further designed as signal- cocrystals, the rigid structure is conducive to reducing
visualized information encryption. nonradiative decays, and thus improving the RTP emission.17-18
Furthermore, the construction of ratiometric cocrystal systems
Purely organic room-temperature phosphorescence (RTP) by the same assembled units but different ratios is also promising
luminophores with long-lived triplet excited states have become to tune the orientation and aggregation states of the RTP
more and more attractive in the fields of bioimaging, sensors, molecules, which facilitates the adjustable RTP color and
optical recording and anti-counterfeiting.1-4 RTP color is one of efficiency. As a result, we believe that the use of a ratiometric
the most important parameters for evaluating these organic RTP cocrystallization strategy can be considered as a facile and cost-
luminophores, and thus the tunable RTP is highly desirable for
multicolor displays. In general, researchers need to design and
synthesize various organic molecules with suitable heteroatoms
(such as O, S, N or P) to meet the demands for obtaining different
emission colors, which is deemed to be relative laborious, time-
consuming, and sometimes unpredictable. 5-7 Recently, crystal
engineering have been proved as an effective and flexible
approach to realize different RTP lifetimes by adjusting the
stacking modes and the inter/intramolecular interactions. 8-11
Given that both emission wavelength and decay lifetime of these
luminophores are related to the properties of triplet excitons, we
reasoned that the crystal engineering strategy has also great
potential to expand the color range of RTP emission.
Molecular cocrystals, a large family of multicomponent
crystalline materials, have the ability to regulate many
physiochemical properties, such as solubility, stability, and

1.Beijing Key Laboratory of Energy Conversion and Storage Materials,

College of Chemistry, Beijing Normal University, Beijing 100875, P. R. China
E-mail: yandp@bnu.edu.cn Fig. 1 The constructed ratiometric cocrystals (BTA-ME-1 and BTA-ME-
2.College of Chemistry and Molecular Engineering, Zhengzhou University,
Zhengzhou 450001, China 2), and the calculated molecular orbital diagrams which exhibit the
energy transferring from ME to BTA.
Electronic Supplementary Information (ESI) available. See DOI: 10.1039/x0xx00000x

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Fig.2 The solid-state excitation, prompt and delayed PL spectra of BTA-
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ME-1 (a) and BTA-ME-2 (b). (c) The corresponding positions in CIE
chromaticity coordinates. (d) The solid-state excitation spectra of ME,
BTA and the ratiometric cocrystals.
effective method to realize color-tunable RTP emission from the
perspective of crystal engineering and molecular self-assembly.
To prove this hypothesis, in this work, we designed and
synthesized two cocrystals by choosing melamine (ME) and
1,2,4-benzenetricarboxylic acid (BTA) as the basic co-
assembled units. The resulting ratiometric cocrystals of BTA-
ME-1 and BTA-ME-2 are assembled with the molar ratios of 1:1
and 2:1 of BTA to ME. ME is an ideal component which can
form a series of cocrystals through abundant hydrogen bonds and
π-π interactions with other co-formers. The n→π* transition of
carboxylic group of BTA is in favor of displaying
phosphorescence, and its asymmetric molecular structure can
increase the assembly diversity of cocrystals. 19-22 In these
ratiometric cocrystals, the suitable energy levels between the
assembled units are advantageous to the energy transfer from ME
to phosphor BTA, as confirmed by density functional theory
(DFT) calculation (Fig. 1).23 Benefitting from the different
stacking modes and electronic structures of ratiometric
cocrystals, the H-aggregation and J-aggregation of BTA
molecules appear in BTA-ME-1 and BTA-ME-2, leading to
green and yellow RTP colors, respectively. Therefore, as an
alternative of traditional organic synthesis, this work proposes a
ratiometric cocrystallization strategy to realize multicolor RTP
emission and lifetimes, which further shows application prospect
in the domains of information encryption and data storage. 24
Firstly, two bulk cocrystals were synthesized by a green, rapid
and facile hydrothermal method (Fig. S1 in ESI†). Powder X-ray
diffraction (PXRD) prove that the prepared products are single
phase (Fig. S2 in ESI†), confirming the high purity of the
cocrystals. Single-crystal X-ray diffraction analyses demonstrate
that both BTA-ME-1 and BTA-ME-2 crystallize in a triclinic
crystal system with the space group of P-1 (Table S1 in ESI†).
In each layer of the cocrystals, BTA molecules form almost the
same type of hydrogen bonds with neighboring three ME
molecules and three water molecules (Fig. S3 and Table S2 in
2 | J. Name., 2012, 00, 1-3
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ESI†). The formation of strong hydrogen bonds is alsoViewconfirmed
Article Online
by their FT-IR spectra (Fig. S4). The stacking modes of phosphor
DOI: 10.1039/D0CC02730H
BTA in two ratiometric cocrystals are totally different: BTA
molecules in BTA-ME-1 take “face to face” stacking mode with
the central distance of 3.628 Å between adjacent layers and
relative orientation of 69.09o, which is consistent with the way
of forming H-aggregation; while the another stacking mode,
namely “head to tail”, appears in BTA-ME-2 with a longer
central distance of 5.500 Å and relative orientation of 31.93o,
which is more inclined to be J-aggregation (Fig. S5 in ESI†).5,25
Thermogravimetric analysis and differential scanning
calorimetry (TGA-DSC) measurements reveal that the thermal
behaviors of BTA-ME-1 and BTA-ME-2 are much alike, i.e., the
very close temperature for every endothermic process (Fig. S6 in
ChemComm Accepted Manuscript
ESI†). Their weights are almost constant from 300 K to 447 K,
which indicates the cocrystals are highly stable under ambient
atmosphere, and ensures them for practical application.
Therefore, the stacking mode and relative orientation of two
ratiometric cocrystals are alternated obviously, which would
further influence their RTP emission.
In order to detect the RTP performances between two
ratiometric cocrystals, a series of photophysical tests were
systematically studied. The photoluminescence (PL) spectra of
ratiometric cocrystals were measured at room temperature
(Table S3 in ESI†). The prompt PL spectra exhibit that
fluorescence emission peaks of BTA-ME-1 and BTA-ME-2 are
located at 458 nm and 379 nm, respectively. Meantime, the
delayed PL spectra, detected after 0.1 ms of excitation,
demonstrate that the green RTP emission of BTA-ME-1 is
located at 505 nm with the color coordinate of (0.25, 0.36), while
the RTP of BTA-ME-2 is red-shifted to 515 nm showing yellow
emission with the color coordinate of (0.33, 0.49) (Fig. 2a-c).
The solid-state excitation spectra of BTA-ME-1, BTA-ME-2 and
BTA almost overlapped with each other at 360 nm (Fig. 2d),
indicating that the PL of ratiometric cocrystals is derived from
the phosphor BTA rather than ME. It is worth noting that both
the tail excitation and the RTP emission of BTA-ME-2 are red-
shifted compared with BTA-ME-1, which is consistent with the
narrow energy gap of J-aggregation of BTA in BTA-ME-2; on
the other hand, the H-aggregation of BTA in BTA-ME-1 exhibits
blue-shifted RTP emission due to its larger energy gap,8 which
can also be confirmed by calculating the band structures and
density of states (DOS) of these ratiometric cocrystals with the
Fig.3 (a) The solid-state excitation, prompt and delayed PL spectra of
BTA. (b) The lifetime decay profiles of BTA, BTA-ME-1 and BTA-ME-2.
This journal is © The Royal Society of Chemistry 20xx
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band gap values of 3.10 eV for BTA-ME-1 and 2.98 eV for BTA-
ME-2 (Fig. S7 and Fig. S8 in ESI†).
Then, in order to figure out why multicolor RTP emission can
be realized on the established ratiometric cocrystal platforms, the
interaction between the co-formers (ME and BTA) is further
studied in terms of their electronic structures and energetic
match. Firstly, by forming strong multiple hydrogen bonds and
π-π interactions with ME, the structural rigidity of crystals is
enhanced and the triplet excitons of phosphor BTA can be
effectively stabilized in ratiometric cocrystals, thus limiting the
nonradiative decays and improving the RTP properties (Fig.
3).11,26-28 Molecular orbital calculations reveal that the highest
occupied molecular orbitals (HOMO) and lowest unoccupied
molecular orbitals (LUMO) are mainly populated on ME and
BTA, respectively, which denotes the energy transfer (ET)
process from donor (ME) to acceptor (BTA), and will finally
impact the RTP emission. Experimentally, the absorption peak
of BTA overlaps with the emission peak of ME at 308 nm,
implying an appropriate energetic match between energy donor
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ME and energy acceptor BTA (Fig. S9 in ESI†). Because the
distance in donor-acceptor pair is less than 1 nm and the
symmetry of ME is able to offer suitable molecular orientation,
the type of ET can be ascribed to the Förster resonance energy
transfer (FRET). According to the equation E p = 1 – τDA/τD (τDA
and τD represent the lifetime values of the energy donor in the
presence and absence of the energy acceptor, respectively), the
FRET efficiency of BTA-ME-1 and BTA-ME-2 are calculated
to be 81.13% and 78.97%, respectively (Fig. S10 in ESI†). To
Fig.4 The diagram depicting the process of signal-visualized encryption
technology by using BTA-ME-2 as the encrypted materials.
This journal is © The Royal Society of Chemistry 20xx
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the best of our knowledge, such efficiencies are higher than most
View Article Online
of the state-of-the-art FRET systems, particularly for molecular
DOI: 10.1039/D0CC02730H
cocrystals.25 Additionally, the FRET efficiency between ME and
BTA in BTA-ME-1 is higher than that in BTA-ME-2, which can
be related to the fact that the energy level of donor ME is closer
to the acceptor BTA with H-aggregation type in BTA-ME-1, and
accordingly the ET process will be more efficient. As a result,
the corresponding RTP lifetime and quantum yield of BTA-ME-
1 (1.0 ms and 7.86%) are all higher than those of BTA-ME-2 (0.7
ms and 5.24%). Therefore, in these ratiometric cocrystal
systems, ME molecule not only acts as the cocrystal unit to
stabilize the crystal structures, but also continuously transfer
energy as the donor to prolong the triplet exciton lifetimes of the
energy acceptor (BTA), and improves the quantum yield of
ChemComm Accepted Manuscript
cocrystal as well.
Interestingly, the extended RTP lifetime is beneficial to time-
resolved visualization imaging in the application of information
encryption. Herein, we have developed an advanced information
encryption strategy, which is able to integrate the time-resolved
visualization imaging with computer terminal controlling, and
thus improves the accuracy of information encryption. In trial,
the cocrystal BTA-ME-2 is randomly selected as the encrypted
material to operate this encryption platform (Fig. 4). If the
terminal runs under the prompt mode, false information will
appear on the screen and the luminescence of encrypted material
is hardly detected with our naked eyes. However, when we set
the delayed mode with the gating time 0.1 ms on the terminal,
real information can be gained and the bright RTP emission is
easily captured for this mode. So, with synchronous information
processing, the visualized information encryption based on time-
resolved RTP and afterglow emission will be more effective and
precise.
In conclusion, by the combination of the crystal structures,
photophysical tests and theoretical calculations, we proved that
the ratiometric cocrystallization can serve as an effective strategy
to realize multicolor RTP emission and tunable intermolecular
energy transfer by reasonably regulating stacking modes of the
phosphor with the same self-assembled units. Following this
strategy, the synthesized H-aggregation (BTA-ME-1) and J-
aggregation cocrystal (BTA-ME-2) exhibit green and yellow
RTP emission, respectively. Moreover, based on the time-
resolved characteristics of the cocrystal luminophores, we
devised an efficient information encryption platform, which
takes the advantages of visualized imaging with precise terminal
controlling. Therefore, this work not only supplies a facile and
general ratiometric cocrystal strategy to achieve multicolor RTP
emission, but also developed a new signal-visualized encryption
technology by utilizing the RTP cocrystal materials, which may
open up an alternative way to develop various RTP materials
with tunable emission/lifetime/efficiency, and would provide a
great opportunity for applying these encrypted materials in
complex practical environment.
This work was supported by the National Natural Science
Foundation of China (Grant No. 21771021, 21822501, and
22061130206), the Newton Advanced Fellowship
award (NAF\R1\201285), the Fok Ying-Tong Education
Foundation (Grant No. 171008), the Beijing Nova Program
J. Name., 2013, 00, 1-3 | 3
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(Grant No. xx2018115), the State Key Laboratory of Rare Earth
Resources Utilization (RERU2019005), the Measurements Fund
of Beijing Normal University, and the Fundamental Research
Funds for the Central Universities.
Conflicts of interest
There are no conflicts to declare.
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Table of Content DOI: 10.1039/D0CC02730H

ChemComm Accepted Manuscript

Published on 16 June 2020. Downloaded on 6/17/2020 1:49:52 AM.

Color-tunable green and yellow room temperature phosphorescence is realized

through a ratiometric cocrystal strategy.