Photophysics of Cu(I) and Ag(I) compounds showing ... · PDF fileBph 2) powder N N 2 C u P P 2...
Transcript of Photophysics of Cu(I) and Ag(I) compounds showing ... · PDF fileBph 2) powder N N 2 C u P P 2...
![Page 1: Photophysics of Cu(I) and Ag(I) compounds showing ... · PDF fileBph 2) powder N N 2 C u P P 2 O N N B MLCT 1MLCT 3MLCT S 0 T 1 ... Case Study . S1 T1 S0 TADF kBT Combined TADF and](https://reader033.fdocuments.net/reader033/viewer/2022052916/5a7bef1d7f8b9a4d628c6bba/html5/thumbnails/1.jpg)
Photophysics of Cu(I) and Ag(I) compounds showing
efficient thermally activated delayed fluorescence.
Strategies for material design.
Hartmut Yersin
Universität Regensburg, Germany
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Outline
Focus: Design of new emitter molecules for OLEDs
Short introduction to Singlet Harvesting for 100% exciton use
- based on TADF
Strategies how to develop materials with short-lived emission
Important for:
- high emission quantum yield
- increase of device stability
- decrease of roll-off
Several case studies:
- First: focus on Cu(I) complexes
- Then: presentation of extraordinarily efficient Ag(I) materials
Conclusion
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t(T )1
Spins and electron-hole recombination
3 -1DE(S -T ) < 10 cm (0.12 eV)1 1
threetriplet paths 75 % 25 %
singlet
up-/down-ISC
S0
S1
T1
path
k TB
t(TADF)k(S )1
TADF and Singlet Harvesting in OLEDs for 100% exciton use
TADF: Parker 1961OLEDs: Yersin 2006
e
DE(S -T )1 1
k TB
-
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Case Study
Blue-light emitting Cu(I) complex
weak SOC
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T = 300K l max = 464 nm F PL = 90 % t = 13 ms
Cu(pop)(pz2Bph2) powder
NN
Cu2P P
2
O
NNB
MLCT LUMO
HOMO
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T = 300K l max = 464 nm F PL = 90 % t = 13 ms
Cu(pop)(pz2Bph2) powder
NN
Cu2P P
2
O
NNB
MLCT 1MLCT
3MLCT
S0
T1
S1 small E(S1-T1)
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k TB
474 nm
l max l max
464 nm
S 1
T 1
S 0
Cu(pop)(pz BPh ) (powder) - TADF material2 2
25000 20000
400
Em
issi
on in
tensi
ty
450 500 550l
n
nm
30 K 300 K
464800
474 nm
-1cm
-1cm
Czerwieniec R., Yu J., Yersin H.Inorg. Chem. 2011, 50, 8293
t(TADF)13 ms
t(T )1
480 ms
rk increasefactor 35
13 480 ms
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Cu(pop)(pz Bph ) (powder) - Singlet harvesting based on TADF 2 2
B
CuP
22P
N N
N N
O
480 ms 13 ms
-1650 cm
S 1
T 1
S 0
(fit)k TB
0
Em
issi
on d
eca
y tim
e
50 100 150 200 250 K 300
Czerwieniec R., Yu J., Yersin H.Inorg. Chem. 2011, 50, 8293
0
100
200
300
400
500
T emission1
S emission1
480 ms
ms
t(TADF)
13 ms
DE(ZFS)-1<1 cm
(80 meV)
t(phos)
t(T) = 3 + exp [-DE(S -T ) / (k T)] 1 1 B
3k(T →S ) + k(S →S ) exp [-DE(S -T ) / (k T)]1 0 1 0 1 1 B
rk (S →S )1 0
6 -15.3∙10 s (fit)
DE(S -T )1 1
rate increasefactor 35
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For OLED applications
τ (T) =
3 + exp [ E(S1 T1) / (kBT)]
3 k(T1→S0) + k(S1→S0) exp [ E(S1 T1) / (kBT)]
t(300 K) should be as short as possible high emission quantum yield increase of device stability decrease of roll-off
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For OLED applications
τ (T) =
3 + exp [ E(S1 T1) / (kBT)]
3 k(T1→S0) + k(S1→S0) exp [ E(S1 T1) / (kBT)]
t(300 K) should be as short as possible high emission quantum yield increase of device stability decrease of roll-off
How to realize?: DE(S1-T1) as small as possible k(T1→S0) as large as possible k(S1→S0) as large as possible
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Summary of requirements
S1
T1
S0
E k(S1↔S0) large
k(S1)
challenge
S0
T1
S1
k(T1→S0) large
phos k(T1)
High SOC
S1
T1
S0
pre-exponential factor
ΔE small
next Case Study
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S 1
T 1
S 0
TADF
k TB
Combined TADF
and phosphorescence
phosk(T )1
k(T →S ) large1 0
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SOC governed by HOMO – (HOMO-1) energy difference
Energy difference from
simple DFT calculations
Energy difference
governs SOC
LUMO
HOMO
HOMO-1
MLCT 1 MLCT 2
*
d1
d2
1,3MLCT 1 1,3MLCT 2
SOC
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S0
S1
S2
T1
T2
1MLCT2
3MLCT2
1MLCT1
3MLCT1
SOC SOC
Energy State Diagram
rk (T -S )1 0 borrowsallowedness from
S ↔S2 0
HOMO-1 d , p2 2
HOMO d , p1 1
LUMO p*
MLCT 1 MLCT 2
DE
Orbital Diagram
SOC routes for energy states
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0 0.5 1.0 1.5 2.0
0
1
2
3
4
5
4-1
k(
) =
1/t
(T)
[10
s]
1
exp
eri
men
tal
T1
D(HOMO - (HOMO-1)) [eV] from DFT
Triplet decay rate vs. (HOMO) - (HOMO-1) energy for different Cu(I) complexes
Cu Cl (P^N)2 , strong SOC2 2
Cu(POP)(pz Bph ), weak SOC2 2
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Case Study
Di-nuclear Cu(I) complex with
very strong SOC
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NPh2P
Cu Cu
N PPh2
ClCl
T = 300K l max = 510 nm F PL = 92 % t = 8 ms
Cu2Cl2(N^P)2 powder
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Emission decay of Cu Cl (N^P) powder2 2 2
Results
· Broad unstructured emission
· Mono-exponential decay Þ fast equilibration· Different states involved
Boltzmann-like distribution
T. Hofbeck, U. Monkowius, H. YersinJACS 2015, 137, 399
Þ
Fit data Þ
1000
100
10
Deca
y tim
e [µ
s]
Temperature [K]
101 100
TADFT Phos.1ZFS of T1
N P
Cu Cu
P2
2
Cl Cl
N
13
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T. Hofbeck, U. Monkowius, H. YersinJACS 2015, 137, 399
From the fit:Energy level scheme and decayconstants of Cu Cl (N^P) powder2 2 2
Results· t(S ) = 1
·
· TADF effective
Þ emission effective
40 ns-1
DE(S -T ) = 930 cm1 1
· SOC largeT 1
S0
42 µs
-1930 cm
S1
T1 II
3.5 ms
III
I
T1}7
10 µs
26 µs
30 µs
-1 cm
15
tav TADF
fastISC
ZFS
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New harvesting mechanism beingeffective for high SOC compounds
JACS 2014, 136, 16032JACS 2015, 137, 399
S0
k TB
TADF + tripletemitter
S0
S1
T1
TADFpath
k TB
Conventional TADF-onlyemitter
DE(S -T )1 1
T1
S1
T + TADF pathscombined
1
42 µs 10 µs
8 µs
Highlights
· two radiative decay paths· Þ shorter overall emission decay· Þ new strategy to reduce roll-off effects
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Summary of requirements
S1
T1
S0
E k(S1↔S0) large
k(S1)
challenge
S0
T1
S1
k(T1→S0) large
phos k(T1)
High SOC
S1
T1
S0
pre-exponential factor
ΔE small
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S 1
T 1
S 0
TADF
k TBDE(S -T )1 1
Case Study
Cu(I) compound with very
small DE(S -T ), and very weak SOC1 1
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T = 300K l max = 535 nm F PL = 70 %
t(TADF) = 3.3 ms
Case Study: Cu(dppb)(pz2Bph2) powder
NN
Cu2P P
2
NNB
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S 1
T 1
S 0
DE(S -T )1 1
1MLCT
3MLCT
Cu(dppb)(pz Bph )2 2
T geometry, B3LYP/def2-svp1
NN
Cu2P P
2
NNB
LUMO
HOMO
MLCT
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1200 ms
3.3 ms
time [ms]wavelength [nm]
inte
nsi
tyin
tensity
counts
counts
300 K
30 K
S 1
T 1
S 0
TADF
k TB
548 nm1200 msphos
535 nm3.3 ms
R. Czerwieniec, H. Yersin; Inorg. Chem. 2015, 54, 4322
13 nm
Cu(dppb)(pz Bph ) powder - Emission spectra and decay2 2
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Cu(dppb)(pz Bph ) powder2 2
t(T) = 3 + exp [-DE(S -T ) / (k T)] 1 1 B
3k(T →S ) + k(S →S ) exp [-DE(S -T ) / (k T)]1 0 1 0 1 1 B
1200 ms 3.3 ms
S 1
T 1
k TB
t(TADF)t(phos)r
k (S →S )1 06 -1
3.9·10 sfit
DE(S -T )1 1
rate increase
factor ≈ 250
1200 ms
phos mainly TADF TADF
Complecx 2
t(TADF) 3.3 ms
0 50 100 150 200 250
300 K
deca
y tim
e [m
s]
temperature [K]
300
600
900
1200
80 K30 K
fit
DE(S -T )1 1-1
370 cm(46 meV)
-1370 cm46 meV
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Remarkable results for Cu(dppb)(pz2Bph2)
Very small E(S1-T1) = 370 cm
-1
short (TADF) = 3.3 s
Very long (T1→S0) = 1200 s
SOC weak, not induced by S1
Obviously, no significant SOC between S1 and T1
Increase of the decay rate by the TADF effect
250phosk
TADFk
We found: small E(S1-T1)
However, combined with small k(S1→S0)
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Challenge
small E(S1-T1)
small kr(S1→S0)
further reduction of (TADF) possible?
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Relation between kr(S1-S0) and DE(S1-T1)
2
LH01r r rr const)SS(k
radiative rate
1L2H12
2L1H
11
rrr
1rrkonst
TSE
D
exchange interaction
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S0
T1
S1
T1
S1
S0
HOMO HOMO LUMOLUMO
DE(S -T )1 1
small
rk (S -S )1 0
small
rk (S -S )1 0
large
DE(S -T )1 1
large
Schematic illustration
rRelation between k (S -S ) and DE(S -T ) 1 0 1 1
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200 400 600 800 1000 1200 1400
0
10
20
30
40
50r
6-1
k(S
) [1
0 s
]1
-1ΔE(S -T ) [cm ]1 1
1
2
3
4
5
6
7
8
9
10
11
12
13
14 16
17
18
19
15
Relation between and r
k (S -S )1 0 DE(S -T )1 1
Radiative rate versus
for Cu(I) complexes. Exponential fit function.
rk (S →S )1 0 DE(S -T )1 1
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Relation between kr(S1-S0) and DE(S1-T1)
Compound ΔE(S1-T1)
[cm1]
t(S1)
[ns]
ΦPL
(300 K)
kr(S1)
[106 s1]
1 Cu2I2[MePyrPHOS)(Pph3)2 270 570 0.97 1.7
2 Cu(dppb)(pz2Bph2) 370 180 0.70 3.9
3 [Cu(µ-Cl)(PNMe2)]2 460 210 0.45 2.1
4 [Cu(µ-Br)(PNMe2)]2 510 110 0.65 5.9
5 [Cu(µ-I)(PNMe2)]2 570 90 0.65 7.2
6 Cu2Cl2(dppb)2 600 70 0.35 5.0
7 [Cu(µ-I)(PNpy)]2 630 100 0.65 6.5
8 Cu(pop)(pz2BPh2) 650 170 0.9 5.3
9 Cu(pop)(tmbpy)+ 720 160 0.55 3.4
10 (IPr)Cu(py2-BMe2) 740 160 0.76 4.8
11 [Cu(PNPtBu)]2 786 138 0.57 4.1
12 Cu2I2(MePyrPHOS)(dpph) 830 190 0.88 4.6
13 Cu2Cl2(N^P)2 930 40 0.92 23
14 CuCl(Pph3)2(4-Mepy) 940 47 0.99 21
15 Cu(dmp)(phanephos)+ 1000 40 0.80 20
16 Cu(pop)(pz4B) 1000 80 0.9 11
17 CuBr(Pph3)2(4-Mepy) 1070 41 0.95 23
18 CuI(Pph3)2(4-Mepy) 1170 14 0.66 47
19 Cu(pop)(pz2BH2) 1300 10 0.45 45
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Summary of requirements
S1
T1
S0
E k(S1↔S0) large
k(S1)
challenge
S0
T1
S1
k(T1→S0) large
phos k(T1)
High SOC
S1
T1
S0
pre-exponential factor
ΔE small
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S0
k TB
- New TADF materials required- Ag(I) complexes suited?
S0
S1
T1
t(TADF)„long“
k TB
Traditional TADFcomplexes
T1
S1
t(TADF)short
Sn
DE(S -T )1 1
small
CI of states
Efficient configuration interaction to increase r
k (S →S )1 0
DE(S -T )1 1
small
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p* (ligand)
p (ligand)
4d (Ag)
1 3small DE( MLCT- MLCT)
Frequent material properties:
Cu(I) complexes Ag(I) complexes
LC
p* (ligand)
p (ligand)
3d (Cu)
MLCT
TADF
1 3large DE( LC- LC)
No TADF
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p* (ligand)
p (ligand)
4d (Ag)
SuggestionUse of electrondonating ligand
Material design - TADF for Ag(I) complexes
LC
p* (ligand)
p (ligand)
4d (Ag)
MLCT
ResultAg(I) complex with TADF
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S 1
T 1
S 0
TADF
k TB
Case Study
Ag(I) compounds with very
rhigh k (S →S )1 0
rk (S -S )1 0
large
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Ag(phen)(P2-nCB)
Calculation: MO62X/def2-SVP, T1 optimized, gas phase
strongly electron donating ligand
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F PL = 36 %
tr(TADF) = 5.3 ms
Ag(phen)(P2-nCB) powder
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F PL = 36 %
tr(TADF) = 5.3 ms
Ag(phen)(P2-nCB) powder
Why only 36 % ?
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Fundamental relations
radiative rate
fSrSk
k
1
kkk
k
2
10r
r
r
r
nrr
r
PL
oscillator strength
2
21nrk
vibrational wavefunctions
Important messages for large PL
• knr: as small as possible• f, kr(S1-S0): as large as possible
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Extensive flattening distortion upon excitation
ground state S0 geometry excited state T1 geometry
Ag(phen)(P2-nCB)
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F PL = 36 %
tr(TADF) = 5.3 ms
lmax = 575 nm
Ag(phen)(P2-nCB) Ag(mbp)(P2-nCB) Ag(dmp)(P2-nCB) Ag(dbp)(P2-nCB)
70 %
2.9 ms
535 nm
78 %
3.2 ms
537 nm
100 %
1.4 ms
526 nm
Quantum Yield
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Smaller flattening distortion
ground state S0 excited state T1
Ag(dbp)(P2-nCB)
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F PL 36 %
tr(TADF) 5.3 ms
krexp.(S1→S0)
fTD-DFT(S1→S0) 0.024
Ag(phen)(P2-nCB) Ag(mbp)(P2-nCB) Ag(dmp)(P2-nCB) Ag(dbp)(P2-nCB)
70 %
2.9 ms
2.2·107 s-1
0.048
78 %
3.2 ms
2.2·107 s-1
0.042
100 %
1.4 ms
5.6·107 s-1
0.0536
S1↔S0 allowedness
very short t(TADF) = 1.4 msrelated to the high oscillator strength
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Geometry and oscillator strength
A Ag(dbp)(P2-nCB) TD-DFT: f = 0.0536calculated geometry
B Ag(phen)(P2-nCB) TD-DFT: f = 0.0687geometry fixedto geometry of A
The geometry determines the allowedness and not the phen-substitutionsLevel of theory: MO62X/def2-svp
ground state S0 geometry excited state T1 geometry
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200 400 600 800 1000 1200 1400
0
10
20
30
40
50r
6-1
k(S
) [1
0 s
]1
-1ΔE(S -T ) [cm ]1 1
1
2
3
4
5
6
7
8
9
10
11
12
13
14 16
17
18
19
15
Relation between and r
k (S -S )1 0 DE(S -T )1 1
Radiative rate versus r
k (S →S )1 0 DE(S -T )1 1
for Cu(I) complexes. Exponential fit function.
Ag(dbp)(P -nCB)2
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Case Study
Ag(dbp)(P2-nCB)
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Ag(dbp)(P2-nCB) powder
Shafikov, Suleymanova,Czerwieniec, and YersinChem. Mater. 2017, 29, 1708
DE 10 2016 115 633.7
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Ag(dbp)(P2-nCB) powder
Shafikov, Suleymanova,Czerwieniec, and YersinChem. Mater. 2017, 29, 1708
DE 10 2016 115 633.7
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Summary and guidelines for short (TADF)
Extremely small E(S1-T1) is not required
High allowedness of the S1→S0 transition is more
important
The S1 state must experience mixings with
higher lying Sn states
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Conclusion
Systematic understanding of photophysical properties
design of new and efficient materials
TADF optimization
- E(S1-T1) moderately small
- S1→S0 allowedness as high as possible
Material record: PL(TADF) = 100 %, (TADF) = 1.4 s
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Thanks to my group
Dr. Rafal Czerwieniec
Dr. Thomas Hofbeck
Dr. Markus Leitl
Dr. Larisa Mataranga-Popa
Alexander Schinabeck, M. Sc.
Alfiya Suleymanova, M. Sc.
Marsel Shafikov, M. Sc.
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We acknowledge the financial
support by the BMBF
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