Aerobic Solid State Red Phosphorescence from Benzobismole Monomers and Patternable Self-Assembled Block Copolymers

Article abstract of DOI:10.1002/anie.201809357

The synthesis of the first bismuth-containing macromolecules that exhibit phosphorescence in the solid state and in the presence of oxygen is reported. These red emissive high molecular weight polymers (>300 kDa) feature benzobismoles appended to a hydroc

Full text of DOI:10.1002/anie.201809357

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Accepted Article
Title: Aerobic Solid State Red Phosphorescence from Benzobismole
Monomers and Patternable Self-Assembled Block Copolymers
Authors: Sarah Parke, Emanuel Hupf, Gunwant Matharu, Inara de
Aguiar, Letian Xu, Haoyang Yu, Michael Boone, Gabriel de
Souza, Robert McDonald, Michael Ferguson, Gang He, Alex
Brown, and Eric Rivard
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201809357
Angew. Chem. 10.1002/ange.201809357
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Aerobic Solid State Red Phosphorescence from Benzobismole
Monomers and Patternable Self-Assembled Block Copolymers
Sarah M. Parke,[a] Emanuel Hupf,[a] Gunwant K. Matharu,[a] Inara de Aguiar,[b] Letian Xu,[c] Haoyang
Yu,[a] Michael P. Boone,[a] Gabriel L. C. de Souza,[b] Robert McDonald,[a] Michael J. Ferguson,[a] Gang
He,*, [c] Alex Brown,*, [a] and Eric Rivard*, [a]
Abstract: The synthesis of the first bismuth-containing
macromolecules that exhibit phosphorescence in the solid state and
in the presence of oxygen is reported. These red emissive high
molecular weight polymers (> 300 kDa) feature benzobismoles
appended to a hydrocarbon scaffold, and were built via an efficient
ring-opening metathesis (ROMP) protocol. Moreover, our general
procedure readily allows for the formation of cross-linked networks
and block copolymers. Attaining stable red phosphorescence with
non-toxic elements remains a challenge and thus our new class of
soluble (processable) polymeric phosphor is of great interest.
Furthermore the formation of bismuth-rich cores within organic-
inorganic block copolymer spherical micelles is possible, leading to
patterned arrays of bismuth in the film state.
phosphorescent polymers are of particular interest for
optoelectronic devices due to the simplification of device
fabrication via solution processing,[9] while block copolymers
allow the formation of higher-order (including metallized)
structures of controllable composition.[10]
It is challenging to prepare red emitting phosphorescent
materials that operate in the presence of O2, a well-known
quencher of phosphorescence. Red emission is highly sought
for bioimaging applications, wherein interfering background
fluorescence (of short wavelength blue and green light) can be
readily filtered away from the red emission of the dye.[1c,1d,11]
However, in general, one sees a dramatic reduction of quantum
yield as longer wavelengths of light are emitted due to an
increase in non-radiative decay rate (Energy Gap Law).[12] To
combat oxygen quenching, one can slow down O2 diffusion by
promoting molecular aggregation,[4,13] or by-pass non-radiative
processes through establishing photoinduced metal-metal
bonding in the solid state.[14] However, a general drawback is the
need for tailored intermolecular interactions (such as Br---H
bonding)[15] which cannot always be designed a priori. In this
Communication we report the modular synthesis of bismuth-
containing orange and red phosphorescent molecules and
polymers with negligible oxygen quenching in the solid state
(Figure 1). We also show that block copolymers of controllable
bismuth content can be made, and that assembly of these
copolymers into spherical micelles with bismuth-rich (metallized)
cores is possible. The synthetic tools outlined provide a general
route to a wide swath of new long-lifetime emitters for possible
bioimaging and OLED applications, while the ability to organize
bismuth into localized arrays via block copolymer assembly
opens the door for the production of Bi nanodot seeds for
patterned semi-conductor nanowire growth.[16]
π-Conjugated materials containing p-block elements have found
applications as integral components of solar cells, transistors,
OLEDs, and, more recently, as luminescent dyes for
bioimaging.[1] To date, the vast majority of these materials
contain lighter p-block elements (e.g. B, Si, S, and P).[2]
Encouraging recent synthetic advances have enabled the
incorporation of heavier main group elements into cyclic π-
frameworks leading to novel properties[1b,3] such as room
temperature phosphorescence (RTP).[4] Achieving efficient and
stable phosphorescence in the condensed phase remains a
cornerstone of OLEDs,[5] wherein expensive, and potentially
toxic, transition metal-containing complexes are generally used
to promote population of emissive excited triplet states via the
“heavy element effect”.[6] Despite a promising early report by
Ohshita and coworkers[7] on the detection of dual fluorescence
and phosphorescence from dithienylbismoles, heterocyclic
bismuth compounds have been scarcely explored as potential
emitters of low toxicity,[8] largely due to a lack of suitable
synthetic methods for their preparation. Furthermore,
[a]
S. M. Parke, Dr. E. Hupf, G. K. Matharu, H. Yu, Dr. M. P. Boone, Dr.
R. McDonald, Dr. M. J. Ferguson, Prof. Dr. A. Brown, Prof. Dr. E.
Rivard
Department of Chemistry
University of Alberta
Figure 1. [Left] Generic benzobismole structure showing the sites of easy
modification due to our modular synthesis; [Right] Perfluorinated
benzobismole (R = Ph; Rʹ = C6F5) 6 used as an ink to draw on filter paper and
crystals of the phenylated benzobismole 3 (R and Rʹ = Ph), both illuminated
with 365 nm light in air at room temperature.
11227 Saskatchewan Dr., Edmonton, Alberta, T6G 2G2 (Canada)
E-mail: alex.brown@ualberta.ca
E-mail: erivard@ualberta.ca
Homepage: http://www.chem.ualberta.ca/~erivard
I. de Aguiar, Prof. Dr. G. L. C. de Souza
Departamento de Química
Universidade Federal de Mato Grosso
Cuiabá, Mato Grosso, 78060-900 (Brazil)
L. Xu, Prof. Dr. G. He
Frontier Institute of Science and Technology
Xi'an Jiaotong University
Xi'an, Shaanxi Province 710054 (People's Republic of China)
E-mail: ganghe@mail.xjtu.edu.cn
[b]
[c]
Following
a
modified Fagan-Nugent protocol,[17a] the
arylated benzozirconacycles 1 and 2 were combined with the
bismuth(III) dihalides ArBiCl2 (Ar = Ph or ArROMP; Scheme 1)
leading to the formation of the desired benzobismoles 3–6. To
facilitate Zr/Bi exchange, 10 % CuCl was added, as reported
previously by Takahashi and coworkers to form stannoles.[17b]
The ArBiCl2 reactants were generated in situ by the ligand
scrambling of triarylbismuthine and 2 equiv. of BiCl3.[7b]
Supporting information for this article is given via a link at the end of
the document.
1
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slightly lower than in the respective fluorinated benzobismoles 4
(2.5%) and 6 (1.6%); the possible increased quantum yield in 4
and 6 may arise from added restriction in molecular motion
imposed by the perfluorinated aryl groups. In accordance with
this postulate, the 19F{1H} NMR spectra of 4 and 6 indicate that
one of the C6F5 rings exhibits restricted rotation in solution (see
Figures S44 and S56).[18] There was no significant increase in
quantum yield upon measurement under an Ar atmosphere
(Figure S26). The observed resistance to oxygen quenching
may be due to limited oxygen diffusion through the aggregates.
Scheme 1. Synthesis of the benzobismoles 3 – 6.
The molecular structures of the perphenylated
benzobismole 3 and its fluorinated counterpart 4 are depicted in
Figure 2.[18] In each structure the peripheral aryl rings fan out
from the central bismole ring in a propeller-like fashion and
prevent close packing of the central bismole rings [closest Bi---Bi
contacts > 5.0 Å]. However each of the canted aryl rings forms
close interactions with the rings of neighboring molecules that
presumably limit intramolecular rotations in the crystalline state.
The sum of the bond angles at the Bi centers [270.3(2)° in 3;
264.4(2)° in 4] indicate high s-character of the lone pair, and
partially explains the air-stability of these compounds.[7b]
A
racemic sample of 3 could be separated into its constituent
isomers by chiral HPLC, while no signs of racemization in 10%
2-propanol in hexane was noted for either purified enantiomer
(Figure S36).[18]
Figure 3. Solid state emission and excitation spectra of films made from drop-
casting hexanes suspensions of benzobismoles 3 (a) and 4 (b); all data
recorded in air at room temperature. For related spectra for the aryl
norbornene-capped benzobismoles 5 and 6 see the ESI (Figure S28).[18]
Figure 2. Molecular structures of 3 (left) and 4 (right) with ORTEPs at the
30 % probability level. Selected bond lengths [Å] and angles [°]: 3: Bi-C1
2.256(3), Bi-C4 2.221(3), Bi-C11 2.260(4), C2-C3 1.482(5); C1-Bi-C4 78.6(2),
C11-Bi-C1 96.8(2), C11-Bi-C4 95.0(2). 4: Bi-C1 2.238(3), Bi-C8 2.265(3), Bi-
C31 2.272(3), C6-C7 1.476(4); C1-Bi-C8 77.7(2), C31-Bi-C1 93.6(2), C31-Bi-
C8 93.1(2).
When the benzobismoles 3 and 4 are drop-cast from THF,
CH2Cl2 or toluene, transparent films are formed which do not
show discernable emission [Figures 4 (inset; right) and S25].[18]
However the opaque films of 3 and 4, prepared from fine
suspensions
in
hexanes,
yield
significantly
brighter
phosphorescence [Figures 4 (inset; left) and S25].[18] Thus,
phosphorescence is highly dependent on the morphology of the
solids, an effect previously noted for tellurophenes.[20]
Accordingly, a drop-cast film of 3 from a hexanes suspension
gave rise to a powder XRD pattern that showed high crystallinity,
and matched that predicted from the single-crystal XRD data
(Figures 4 and S5).[18] Alternatively, the non-emissive film made
from drop-casting a solution of 3 in CH2Cl2 gave rise to a powder
pattern indicative of amorphous packing. These data show that 3
and 4 exhibit not only AIE, but more specifically, crystallization
induced emission (CIE) in which there is a strong correlation
between the crystallinity and the intensity of emission for the
materials.[21, 22]
The perphenylated benzobismole 3 shows red emission in
the crystalline state in air [λem = 610 nm; Figure 3a], and the
introduction of electron-withdrawing C6F5 groups in 4 shifts the
emission color to orange-red [λem = 596 nm; Figures 1 and
3b].[18] Moreover, in THF/water mixtures (40:60 wt. %) these Bi
heterocycles show aggregation induced emission (AIE) (Figure
S24).[18,19] Time-dependent luminescence measurements on
drop-cast films (from hexanes) of 3 and 4, as well as their
norbornene-substituted analogues 5 and 6 (Scheme 1), yield
similar emission lifetimes (τ) in the narrow range of 6.6 to 7.5 µs,
in line with phosphorescence.[4] Absolute quantum yields (Φ) of
bismole samples prepared by drop-casting from hexanes
suspensions were measured and it was found that the Φ of the
phenyl-substituted benzobismoles 3 (0.8%) and 5 (0.7%) were
Time-dependent density functional theory (TD-DFT)
computations were carried out for the Ph and C6F5-substituted
benzobismoles 3 and 4. The predicted absorption maxima at the
2
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(CAM-)B3LYP/cc-pVTZ(-PP) level(s) of theory are in agreement
with experimental UV-vis data.[18] The most intense component
of the absorptions arises from a HOMO-LUMO transition of
predominantly C-C π-π* character, while HOMO–1 to LUMO
transitions of substantial oscillator strength and significant orbital
character from Bi were also computed (Figure 5). Previously we
have found that orbital participation from a heavy main group
monomers 5 and 6, polymers P1 and P2 display observable red
luminescence that is bathochromically-shifted by ca. 60 nm from
their respective monomers (Figure S29).[18] It is hypothesized
that an increase in the free volume about the bismole units in the
polymeric materials allows for increased vibrational and
rotational motions (which decrease emission intensity) as well as
possible geometric stabilization of singlet and triplet excited
states, yielding the bathochromic shift in emission. 1H and
19F{1H} NMR data for P1 and P2 gave expectedly broad
resonances, while gel permeation chromatography (GPC) in
THF afforded very high molecular weights (Mn = 2.1 MDa and
PDI = 1.5 for P1; Mn = ca. 600 kDa and PDI = 1.6 for P2).
However, characterization of these polymers was made more
difficult by their limited solubility. Powder XRD analysis of P1
revealed amorphous character and heat annealing films of P1
did not help to increase the crystallinity of the samples (Figure
S6).[18] To improve the solubility of the phosphorescent
element during excitation is
a pre-requisite for efficient
phosphorescence,[7b,23] and thus we have achieved the same
goal in the newly prepared benzobismoles 3 and 4. Moreover,
the computed differences of the zero-point corrected adiabatic
energies (E0-0) of the S0 and T1 states, at their corresponding
optimized geometries, match well with the experimentally
observed phosphorescence energies; similar results were noted
when relativistic effects and spin-orbit coupling were included in
the computations.[18]
polybenzobismoles,
monomers and
the
new
alkylated
arylnorbornene
7
8 (Scheme 2) were prepared. The
corresponding bismuth-free homopolymers P3 and P4 along
with various random copolymers derived from benzobismole (5
and 6) and alkylarene (7 and 8) units in differing ratios were also
synthesized (P5-P9),[18] with a maximum benzobismole content
of 38 mol% (as judged by 1H NMR spectroscopy). Each
copolymer was soluble in THF and CHCl3 with Mn values all
exceeding 150 kDa. TGA analysis indicates thermal stability up
to 250 °C (Figures S13 and S14)[18] for each copolymer. Red
luminescence (λmax = 660 nm) is maintained within the mixed
benzobismole/arylalkyl copolymers (Figures S29);[18] however as
in the benzobismole homopolymers P1 and P2, the emission is
less intense than for the monomeric benzobismoles 5 and 6,
thus precluding the determination of reliable absolute quantum
yields and emission lifetime data.
Figure 4. Powder XRD patterns of films of 3 drop-cast from CH2Cl2 and
hexanes; inset: drop-cast films from hexanes (left) and CH2Cl2 (right) under
ambient light (top) and 365 nm irradiation (bottom).
Figure 5. TD-DFT [B3LYP/cc-pVTZ(-PP)] computed main transitions including
excitation wavelengths and oscillator strengths (f) to low-lying singlet states for
3 (left) and 4 (right) and the associated molecular orbitals; iso-surface values
of +0.02/–0.02 (blue/red).
Scheme 2. Synthesis of homopolymers P1 – P4, and the cross-linking agent
BiArROMP
.
3
To increase the rigidity of the benzobismole polymer matrix,
and possibly enhance phosphorescence, cross-linked polymers
were synthesized. Benzobismole 5 was cross-linked with the
trifunctional bismuthine Bi(ArROMP3) (Scheme 2) using 1 mol%
Grubbs’ 2nd generation catalyst in THF, with ratios that varied
from 25 mol% crosslinker (P10) to 80 mol% (P11). Both P10 and
Ring-opening metathesis polymerization (ROMP) of the
norbornene-substituted benzobismoles 5 and 6 with 1 mol% of
Grubbs’ 2nd-generation catalyst[24] successfully afforded the air-
and moisture-stable homopolymers P1 and P2 (Scheme 2). The
polymerization reactions were found to be rapid with complete
monomer conversion in < 6 min. Though weaker than for
3
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P11 were completely insoluble in common organic solvents,
indicating successful cross-linking. Despite the possible
decrease in intramolecular motion in P10 and P11, similarly
weak red emission was noted as in the non-crosslinked
polymers; enhanced emission was observed upon cooling the
sample to 77 K. These findings suggest that even within the
cross-linked polymer network, the amorphous packing (as
indicated by PXRD analysis; Figure S9)[18] of the benzobismole
side groups allows enough room for internal molecular
motions[25] to contribute to increased rates of non-radiative
decay.
In summary,
a
series of phosphorescent bismuth-
containing polymers and block copolymers have been
synthesized. We introduce a general synthetic strategy to rapidly
generate high molecular weight organic and bismuth-containing
polymers with red phosphorescence, good solubility, and
ordered self-assembly properties. Going forward, we will prepare
new main group element (E)-based block copolymers for the
controlled self-assembly of strongly emissive structures (by
increasing molecular rigidity and via related Zr/E exchange
chemistry), along with optimization of the patterning of
nanodimensional Bi for semi-conductor nanowire growth.[16]
With the goal of obtaining well-defined block copolymers
that self-assemble into ordered micelles,[10] living ROMP was
instigated using Grubbs’ 3rd generation catalyst. As shown in
Acknowledgements
Scheme 3, benzobismole
5 and the arylated norbornene
monomer 8 were sequentially copolymerized to yield the THF-
soluble block-copolymer P12; this block copolymer shows red
This work was supported by NSERC of Canada (Discovery
grants to E.R. and A.B.; CREATE grants/stipends to E.R., S.M.P.
and H.Y.; USRA to G.K.M.; PGS-D to S.M.P.), the Canada
Foundation for Innovation, the Conselho Nacional de
Desenvolvimento Científico e Tecnológico (CNPq) for a special
visiting researcher grant (400179/2014-8). E.H. thanks the
emission at λem = 684 nm (Figure S31) in the film state.[18]
A
a
combination of GPC and 1H NMR analysis indicated
benzobismole/arylalkyl block ratio of ca. 1:6 [Mn = 51 kDa]. As
the arylalkyl block has significantly higher solubility in hexanes
than the benzobismole segment, a combination of hexanes and
THF was used to promote the formation of spherical micelles
containing benzobismole blocks cores surrounded by an
arylalkyl corona. P12 was incubated in 5 % THF in hexanes at a
concentration of 1 mg/mL at 50 °C for 1 hour and then allowed
to cool to room temperature, after which samples were taken for
analysis by TEM and dynamic light scattering (DLS).[18] DLS
indicated the presence of a species with an average diameter of
35 nm while TEM shows discrete spherical regions of high
contrast Bi in the film state (Scheme 3c). Future work will involve
pyrolytic conversion of these organized films to possibly yield
patterned Bi nanodots[16] or bismuth films with potential anti-
bacterial[26] and topological insulating properties.[27]
Deutsche Forschungsgemeinschaft (DFG) for
a research
fellowship (HU 2512/1-1). M.P.B. thanks the Killam Trust for a
postdoctoral fellowship. The computational studies in this work
were made possible by the facilities of the Shared Hierarchical
Academic Computing Network (SHARCNET: www.sharcnet.ca),
WestGrid (www.westgrid.ca), and Compute/Calcul Canada
(www.computecanada.ca). G.H. thanks the Natural Science
Foundation of China (21704081, 21875180) and the Cyrus
Chung Ying Foundation for support.
We also gratefully
acknowledge Wayne Moffat, Jennifer Jones, and Katazhyna
Haidukevich at the University of Alberta analytical laboratory for
the TGA and DSC studies and for helpful discussions. Prof.
Dennis Hall and Dr. Ed Fu are thanked for advice and for
performing the chiral HPLC separation of 3, while we are
grateful to Guoping Li for performing CV measurements. E.R.
also acknowledges the Alexander von Humboldt Foundation for
a fellowship.
Keywords: Bismuth • Heterocycles • Block Copolymers •
Phosphorescence • TD-DFT
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5
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10.1002/anie.201809357
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Turning on Bismuth: The synthesis
of red and orange emitting bismuth-
based phosphors is reported. Our
modular synthetic approach allows for
Sarah M. Parke, Emanuel Hupf,
Gunwant K. Matharu, Inara de Aguiar,
Letiang Xu, Haoyang Yu, Michael P.
Boone, Gabriel L. C. de Souza, Robert
McDonald, Michael J. Ferguson, Gang
He,* Alex Brown,* and Eric Rivard*
rapid
ring-opening
to
metathesis
yield block
polymerization
copolymer spherical micelles that
assemble into organized films with
bismuth-rich, metallized, domains.
[Page No. – Page No.]
Aerobic Solid State Red
Phosphorescence from
Benzobismole Monomers and
Patternable Self-Assembled Block
Copolymers
6
This article is protected by copyright. All rights reserved.