Hydrogen bonding boosted the persistent room temperature phosphorescence of pure organic compounds for multiple applications

Article abstract of DOI:10.1039/c9tc02879j

Persistent room temperature phosphorescence (p-RTP) of pure organic compounds is drawing much attention due to its unique advantages and promising applications in anticounterfeiting, encryption, bioimaging, etc. Achieving efficient p-RTP, however, remains

Full text of DOI:10.1039/c9tc02879j

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J Po lue ran sael od fo Mn aot te rai ad l jsu Cs ht emm ai rs gt ri yn sC
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DOI: 10.1039/C9TC02879J
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ARTICLE
Hydrogen bonding boosted persistent room temperature
phosphorescence of pure organics for multiple applications
†
a,b
†c
d
e
f
c
Received 00th January 20xx,
Accepted 00th January 20xx
Tingting Zhang, Heqi Gao, Anqi Lv, Ziyi Wang, Yongyang Gong, Dan Ding, Huili
Ma,* Yongming Zhang* and Wang Zhang Yuan*b
e
a,b
DOI: 10.1039/x0xx00000x
Persistent room temperature phosphorescence (p-RTP) of pure organic compounds is drawing much attention for its unique
advantages and promising applications in anticonterfeiting, encryption, bioimaging, etc. Achieving efficient p-RTP, however,
remains challenging. In this contribution, we designed and synthesized three benzoic acid-carbazole conjugates, 4-BACZ, 3-
BACZ and 2-BACZ, with strong hydrogen bonding and dimer sturcture in their crystals. Comapred with their ester
www.rsc.org/
p p
counterparts, whose highest RTP efficiency (Φ ) is 2.6%, these acids exhibit significantly boosted Φ of 6.9%, 3.4% and 2.6%
for 4-BACZ, 3-BACZ and 2-BACZ, respectively. Such enhancement should be ascribed to the effective and aboundant
hygrogen bonding in the crystals, which significantly depressed the vibrational dissipations. This effect is also confirmed by
the theoretically calculated much lower reorganization energies. These crystals are also readily fabricated into
biocompatible nanoparticles (NPs) with inherited p-RTP characteristic. Such p-RTP feature of the crystals and NPs endows
them highly promissing for versatile applications. Herein, anticounterfeiting and high resolution in vivo afterglow bioimaging
adopting these materials are demonstrated.
organic compounds are quite low and generally below 5%.42
Such situation is caused by the weak spin-orbital coupling (SOC)
and the difficulty to efficiently imped quenching and
Introduction
Pure organic compounds with persistent room temperature
phosphorescence (p-RTP)
their unique advantages, such as long emission lifetime, low
1
9-24,43,44
nonradiative deactivations.
To reduce spin inhibition,
1
-19
are drawing much attention for
heavy atoms, heteroatoms and aromatic carbonyls are often
1
9-24,45-48
incorporated to promote the SOC.
To depress
2
0-25
cost, easy processability,
and promising applications in
nonradiative dissipations and quenching, relative rigid
environments with good oxygen barrier properties are provided
9
,10,17,26-
bioimaging, sensing, encryption, anticounterfeiting, etc.
3
0
Moreover, apart from conventional conjugated molecules, p-
2
0,37,38,49-51
with methods like crystallization,
doping,
host-guest
and the
Although
1
0,31-33
RTP is also observed from nonconventional luminogens.
3
,19,52
39,53-55
polymer matrix embedding
formation of metal-organic framework (MOF).
However, compared with inorganic and metal-containing
1
7,56
phosphors,3
4-36
pure organic RTP is difficult to accomplish,
great progress has been made in recent years, it remains
challenging for improving the p-RTP efficiency of pure organics.
on account of their forbidden nature and the susceptibility of
triplet excitons.3
7-41
Meanwhile, p-RTP quantum yields of pure
a. School of Materials Science and Engineering, Shanghai Jiao Tong University, 800
Dongchuan Road, Shanghai 200240, China.
b.
Shanghai Key Lab of Electrical Insulation and Thermal Aging, School of Chemistry
and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road,
Shanghai 200240, China. E-mail: ymzhang@sjtu.edu.cn, wzhyuan@sjtu.edu.cn.
State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive
c.
Materials, Ministry of Education, College of Life Sciences, Nankai University, Tianjin
3
00071, China.
d.
Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials
IAM), Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, China. E-
(
mail: iamhlma@njtech.edu.cn.
Department of Materials Science and Engineering, Northwestern University,
Evanston, Illinois 60208, United States.
College of Materials Science and Engineering, Guilin University of Technology, 12
Jiangan Road, Guilin 541004, China.
e.
f.
†
These authors contributed equally.
Electronic Supplementary Information (ESI) available: Detailed synthesis and
Chart 1. Structures of 4-BACZ, 3-BACZ, 2-BACZ and their corresponding esters and the
1
13
characterizations; H and C NMR spectral details; mass spectrometry details; single
crystal structure details; video details; CCDC 1915584–1915586. For ESI and
crystallographic data in CIF or other electronic format see. See
DOI: 10.1039/x0xx00000x
schematic illustration of the dimers in the crystals. PL efficiencies of the crystals (Φ
c
) and
p
their p-RTP efficiencies (Φ ) are also given. The photophysical data of the esters were
adopted from ref [57].
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Very recently, we reported the p-RTP emission of methyl 4-(9H-
carbazol-9-yl)benzoate (4-MBACZ), methyl 3-(9H-carbazol-9-
yl)benzoate (3-MBACZ) and methyl 2-(9H-carbazol-9-yl)benzoate (2-
MBACZ) (Chart 1) from their both crystalline and amorphous states.57
Despite owning moderate photoluminescence (PL) efficiencies
Journal Name
Results and discussion
View Article Online
DOI: 10.1039/C9TC02879J
The target compounds were easily obtained by the hydrolysis
and consequent acidization of corresponding esters (Scheme
1
13
S1, ESI†). They were fully characterized by H and C NMR, high
resolution mass spectrometry (HRMS) (Fig. S1-S9, ESI†) and X-
ray single crystal diffraction analysis (Table S1, ESI†), with
satisfactory results being obtained.
(
6.5~37.6%), their p-RTP efficiencies (Φ
improving the Φ values is of crucial importance to their real-world
applications, which could be realized through rational molecular and
p
) are low (≤2.6%). Further
p
-5
In dilute tetrahydrofuran (THF) solutions (10 M), the
crystal engineering.20-23 In this contribution, to obtain more efficient absorption maxima of three compounds are mainly located at
p-RTP luminogens, we converted the ester groups of MBACZ into 293, 325 and 335 nm (Fig. S10, ESI†), which are similar to the
5
7
corresponding esters. We deduced that the 293 nm peak
belongs to π-π* transitions, and the longer wavelength bands
with well resolved structures should also be ascribed to the π-
carboxyl units. The elimination of the relatively bulky methyl group
is helpful to generate much denser molecular packing in crystals.
Furthermore, the presence of carboxyl moiety is expected to
generate effective hydrogen bonding, which is beneficial to boost
both efficiency and lifetime of p-RTP owing to the stabilization of
π* transitions with hybrid local excited (LE) and charge transfer
CT) states. They emit bright blue light in THF, with PL
maxima/efficiencies of 400 nm/87.7%, 405 nm/29.0% and 422
57
(
triplet excitons. Indeed, all three isomers, 4-(9H-carbazol-9- nm/20.2% for 4-BACZ, 3-BACZ and 2-BACZ (Table 1, Fig. S10,
ESI†), respectively. When dopped in polymethyl methacrylate
m
PMMA) films with 1 wt% fraction, their emission maxima (E )
are at 394, 399 and 407 nm for 4-BACZ, 3-BACZ and 2-BACZ,
respectively (Fig. S11, ESI†), which are close to those of the
corresponding solutions (Table 1). Their lifetimes are 6.5, 12.3
and 7.9 ns, respectively (Table 1, Fig S11, ESI†), and no
yl)benzoic acid (4-BACZ), 3-(9H-carbazol-9-yl)benzoic acid (3-BACZ)
and 2-(9H-carbazol-9-yl)benzoic acid (2-BACZ) exhibit hydrogen
bonded dimer structure with Φ of up to 6.9%, which are remarkably
p
boosted when compared with those of their esters (Chart 1). Their
photophysical properties were thoroughly investigated and the
(
isomeric effect is discussed. Notably, water dispersible nanoparticles noticeable signals could be acquired for the films with a delay
(
d
NPs) prepared from these acids also exhibit p-RTP emission, which time (t ) of 0.1 ms, thus confirming their fluorescent nature.
Their solid emission was further studied. As shown in Fig. 1
and S12 (ESI†), the crystalline solids (Fig. S13, Video S1, ESI†) of
three compounds exhibit blueish-white emission under 365 nm
UV light. After ceasing the irradiation, orange or yellowish-
were used for the in vivo afterglow bioimaging with high signal-to-
background ratio (SBR) of up to 62 being acquired.
Fig. 1 (A) Photographs taken under 365 nm UV light or after ceasing the irradiation, (B) emission spectra and (C) p-RTP lifetimes of the crystals for 4-BACZ, 3-BACZ and
2
-BACZ. (D) Comparison of the Φ
p
values of 4-BACZ, 3-BACZ, 2-BACZ and their corresponding esters.
2
| J. Name., 2012, 00, 1-3
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orange lights lasting for several seconds are observed, which are 2.6%, which are significantly enhanced by 2.7, 4.9 aVinewdA2rt6ic.le0O-fnolinlde
corresponded to their p-RTP. 4-BACZ exhibits a prompt E
m
at
of 0.1 ms, other than the original one,
m
occurs at 549 nm together with a shoulder at ~594
with comparison to the esters (Fig. 1D). DOI: 10.1039/C9TC02879J
4
29 nm. With a t
d
To gain more insights into their photophysical properties,
single crystals of three acids were cultured and their structures
were determined (Figs. 2, 3, Figs. S15, S16, Table S2, ESI†). As
can be seen from Figs. S15 and S16 (ESI†), abundant and
effective intermolecular interactions are present in all crystals.
Taken 2-BACZ for example, OH···O=C (1.835, 1.831 Å)
hydrogen bonds, CH···π (2.898, 2.760, 2.786, 2.835, 2.830 Å),
C=O···OH (2.651, 2.633 Å), O=C···HO (2.729, 2.662 Å),
OH···HO (2.304 Å), CH···O=C (2.691 Å) short contacts and
even π···π (3.321 Å) interactions are found in the crystals (Fig.
S16, ESI†). These strong intermolecular interactions greatly
imped the molecular motions to offer rigidified conformations;
emerging E
nm (Fig. 1B). These results indicate that the emission at 429 nm
comprises of both prompt and delayed fluorescence (PF and
DF), whereas the others should be ascribed to the p-RTP
emission, whose lifetime (<>
determined by the time-resolved emission measurement (Fig.
C).
p
) is 558 ms (at 549 nm) as
1
Table 1 Photophysical properties of 4-BACZ, 3-BACZ and 2-BACZ.
solution
film
crystal
a
b
a
b
a
c
b
Sample
λ
f
<τ>
f
λ
f
<τ>
f
λ
f
λ
p
(nm) <τ>
f
<τ>
p
(
nm)
(ns)
8.0
5.0
4.3
(nm)
393
398
406
(ns)
6.5
(nm)
429
(ns) (ms)
549/594 4.3 558
4
3
2
-BACZ
-BACZ
-BACZ
400
405
422
12.3
7.9
441/484 546/592 13.8 602
444/485 558/599 12.3 568
a
fluorescence peak(s). b fluorescence lifetime. RTP peaks.
c
Similar to 4-BACZ, 3-BACZ and 2-BACZ emit simultaneous PF,
DF and p-RTP. Their prompt emission spectra show the E
41/484 and 444/485 nm for 3-BACZ and 2-BACZ, respectively.
With a t of 0.1 ms, other than above E s, new ones at 546/592
and 558/599 nm associated to the p-RTP emissions are noticed
Fig. 1B). The <> values for 3-BACZ and 2-BACZ crystals were
m
s at
4
d
m
(
p
also determined, which are 602 (at 546 nm) and 568 ms (at 545
nm) (Fig. 1C), respectively. Notably, compared with their
corresponding esters, the fluorescence of the crystalline acids
are obviously bathochromically shifted from 402, 403 and 428
4
9
nm to 429, 442 and 444 nm for 4-BACZ, 3-BACZ and 2-BACZ,
accompanying lifetimes of 4.3, 13.8 and 12.3 ns (Fig. S13, ESI†),
respectively. Such bathochromic shift might be ascribed to the
dimer formation through hydrogen bonding (vide infra), which
extends the effective conjugation length of the compounds.
Their phosphorescence, however, depicts neglectable changes.
To quantitatively evaluate the emission of the crystals, their
Fig. 3 Fragmental molecular packing and exampled hydrogen bonds, π···π
interactions, and short contacts among oxygen atoms of (A) 3-BACZ and (B, C) 2-
BACZ crystals.
c
quantum efficiencies (Φ ) were measured, which are 53.3%,
Fig. 2 Fragmental molecular packing and exampled hydrogen bonds, π···π interactions, and short contacts among oxygen atoms of 4-BACZ
crystals.
1
7.4% and 12.7% for 4-BACZ, 3-BACZ and 2-BACZ, respectively. meanwhile, the crystalline lattices also prevent the molecules
p
The RTP efficiencies (Φ ) were calculated as 6.9%, 3.4% and from contacting with triplet quenchers (i.e. oxygen, moisture),
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Journal Name
thus synergistically generating bright p-RTP emission. Notably, peaks between them. Likewise, owing to the highlyVaiepwpArrtoicalecOhnilninge
there are abundant hydrogen bonds in acid crystals, which are ΔES0T1 values, neglectable shifts of RTP peDakOsI:a1m0.1o0n3g9/oCt9hTeCr02a8c7id9Js
absent in their ester counterparts. Taken 2-BACZ crystals for and the esters are reasonable
.
example, while large amounts of hydrogen bonds are present in
Table 2 Reorganization energy (λ) and ΔES0T1 of 4-BACZ, 3-BACZ, 2-BACZ and 4-MBACZ
crystals.
2
-BACZ crystals, no typical hydrogen bonds exist in 2-MBACZ
5
7
crystals.
The effective hydrogen bonding and other
sample
λ/eV
4-BACZ
0.3740
2.40
3-BACZ
0.3813
2.34
2-BACZ
0.4010
2.46
4-MBACZ
0.4124
2.45
intermolecular interactions provide rigid conformations for 2-
BACZ molecules, thus generating enhanced RTP emission when
compared to that of 2-MBACZ crystals.
ΔES0T1 /eV
Notably, different from the esters, all acids readily form
dimers through hydrogen bonds (Figs. 2 and 3). In particularly,
O···O through space electronic interactions (2.604~2.644 Å),
which would extend the conjugation of the compounds. The
formation of the dimers in the acid crystals well explains why
they exhibit much redder fluorescence than their esters.
Meanwhile, acids also own much smaller torsion angles,
especially for 4-BACZ and 2-BACZ (Figs. S17 and S18, Tables
S3S6, ESI†). For 4-BACZ and 2-BACZ, the mean torsion angles
between carbazole (CZ) and benzoic acid (BA) are 49.7˚ and
Given the high quantum efficiency, long afterglow and
distinct emission colours with UV light on and off, these acids
embrace promising applications in security technologies and in
vivo bioimaging. As depicted in Fig. 5A, under 365 nm UV light,
a blue star made up of the crystals of 4-BACZ is observed, whose
color turns into orange and holds for several seconds after the
stop of irradiation. This process is reversible and can be
repeated for many times. These results illustrate the application
prospective of the acids in multichannel anti-counterfeiting.
It is favourable for compounds with efficient p-RTP to be used
7
7
0.4˚, whereas those for 4-MBACZ and 2-MBACZ are 52.0˚ and
1.5˚. As for 3-BACZ, despite it possesses a much larger mean
9,26-28
for in vivo afterglow imaging,
which can exclude the
nanosecond tissue autofluorescence, thus offering more
reliable observation than traditional fluorescent agents. Owing
to their bright p-RTP in crystals, three acids were fabricated into
NPs through the top-down method by encapsulating the solids
with the amphiphilic copolymer PEG-b-PPG-b-PEG (F127) under
continuous sonication, as demonstrated in Fig. S19A (ESI†). This
approach could take advantage of having nanoscale size and
orderly molecular packing of RTP luminogens. The resulting NPs
of 4-BACZ, 3-BACZ and 2-BACZ can be well dispersed in water
torsion angle between CZ and BA than in 3-MBACZ, it shows a
much smaller mean torsion angle between carboxyl and the
benzene ring (0.8˚, 7.5˚ for 3-MBACZ). Much smaller torsions
also offer better conjugation, which work together with the
dimers to yield red-shifted emissions.
To further elucidate the greatly enhanced Φ of the acids, we
p
calculated the excited-state electronic structures for all acids
and their esters with the time-dependent density functional
Fig. 4 Energy level diagrams of BACZ and 4-MBACZ calculated by the QM/MM model.
theory (TD-DFT) method at the level of B3LYP/6-31G(d), with similar hydrodynamic diameter of 98.7, 101.7 and 110.4
including the energy level diagrams (Fig. 4) and natural nm (Fig. 5BD), respectively. All NPs are highly stable, whose
o
transition orbitals (NTOs) of the lowest triplet state (T
1
) (Fig. sizes are unchanged when stored at 4 C for more than 6 d (Fig.
S19, ESI†). It is shown that the reorganization energies (λ) of 4- S20B, ESI†). These NPs also inherit the p-RTP feature from their
bulky crystals, among which 4-BACZ NPs present the strongest
BACZ, 3-BACZ and 2-BACZ are 0.3740, 0.3813 and 0.4010 eV, being
increased in order, which are also much smaller than that of 4-
MBACZ (0.4124 eV, Table 2). Principally, the smaller λ means the
p-RTP intensity, presumably associated to its highest Φ and
p
relatively good crystallization ability (Fig. 5B-D, inset).
Furthermore, outstanding photo-bleaching resistance and little
roll-offs of RTP intensities could be observed after 8 cycles or 80
min UV irradiation (Fig. S20C and D, ESI†).
Before the in vivo experiment, biological toxicity of the NPs
was evaluated. As demonstrated in Fig. 5E, small amounts of
cells decay after 24 h are noticed with the presence of varying
concentrations of NPs, which indicates their very low
more restricted nonradiative decay rate of T
increase of the Φ from 2-BACZ, 3-BACZ to 4-BACZ, and from esters
to acids (e.g., 0.4124 eV for 4-MBACZ and 0.4010 eV for 4-BACZ). In
addition, the energy differences between S and T states
ΔES0T1) for 4-BACZ (2.40 eV) and 4-MBACZ (2.45 eV) are less
different (Table 2),[57] which determines the less shift of the RTP
1
, which explains the
p
0
1
(
4
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DOI: 10.1039/C9TC02879J
Fig. 5 (A) Demonstration of the anticounterfeiting application of 4-BACZ. Photographs were taken under 365 nm UV light (left) and after ceasing the UV irradiation (right). The
particle size distribution and in vitro phosphorescence imaging (inner)for 4-BACZ (A), 3-BACZ (B), 2-BACZ (C) NPs; (D) Cell viability assay of HeLa cervical cancer cells after staining
with different concentrations of 4-BACZ, 3-BACZ, 2-BACZ NPs; (E) In vivo phosphorescence imaging based on 4-BACZ, 3-BACZ, 2-BACZ NPs.
cytotoxicity. Then live animals test was conducted, with 4-BACZ, counterfeiting and biomedical imaging. The acids NPs were facilely
3
-BACZ and 2-BACZ NPs being subcutaneously injected into the fabricated through the top-down method with inherited p-RTP
live nude mice. The mice were then transported into IVIS emission from their crystals. And moreover, 4-BACZ and 2-BACZ NPs
instrument, exposed to the 365 nm hand-held UV lamp. Images can be used for the in vivo afterglow imaging, with SBR of up to 62,
were immediately taken after moving the lamp under
bioluminescent mode. Since the removal of real time excitation,
the phosphorescence avoided the interference of
autofluorescence from the skin of mouse, allowing the
observation of the unique and relatively clear p-RTP signals of
the NPs in living mouse. Notably, despite no remarkable signals
could be observed for the 3-BACZ NPs in vivo, presumably owing
to their weaker intensity, 4-BACZ and 2-BACZ NPs show clear
afterglow images with high SBR values of 62 and 33 (Fig. S21,
thus allowing the high-resolution imaging free of the interference of
autofluorescence. These results further suggest the promising
prospects of molecular and crystal engineering toward high
performance pure organic p-RTP luminogens for diverse
applications.
Live subject statement
All animal studies were performed in compliance with the
guidelines set by Tianjin Committee of Use and Care of
Laboratory Animals, and in compliance with the National
Standard of the Peoples’ Republic of China called Laboratory
animal-Guideline for ethical review of animal welfare (GB/T
35892-2018), and the overall project protocols were approved
by the Animal Ethics Committee of Nankai University.
ESI†), which are comparable to those of previously reported
examples.58 These results suggest the acid NPs with p-RTP can
be utilized in biomedical imaging.
Conclusions
In summary, we have successfully developed a series of efficient pure
p
organic p-RTP (<> > 0.55 s) phosphors based on carbazole and
benzoic acid moieties. Acidification of the esters of 4-MBACZ, 3-
MBACZ and 2-MBACZ into acids significantly enhanced their
Conflicts of interest
There are no conflicts to declare.
p
phosphorescence efficiencies, with Φ values changing from 2.6%,
0
.7% and 0.1% to 6.9%, 3.4% and 2.6%, affording the amplification of
up to 26-fold. Such remarkable enhancement should be ascribed to
the highly rigidified conformation through hydrogen bonding, which
also results in much lower reorganization energies in crystals, as
indicated by the theoretical results. Such outstanding p-PRT
performances make them applicable in multiple fields, such as anti-
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (51822303, 51473092 and
5
1622305). W.Z.Y. also thanks the support of the medicine-
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Journal of Materials Chemistry C
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DOI: 10.1039/C9TC02879J
Pure organics with p-RTP efficiency enhanced through hydrogen bonding could be prepared into nanoparticles for
in vivo imaging.