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Research Report
Erasmus Internship in SMCT (SupraMolecular Chemistry &
Technology), Faculty of Science and Technology (TNW),
University of Twente.
Synthesis and
Photophysical
Study of Caged
Iridium
Complexes
Departament de Qumica
Universitat Autnoma de Barcelona
Bellaterra (BCN), Spain
University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology
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Abstract
Iridium(III) complexes have attracted great interest during the last years due to their
outstanding luminescence properties, such as high emission intensities, long lifetimes in the
range of s, and color tunability so as to cover a full range of visible colors. These properties
result in a wide field of potential applications.
Nevertheless, Iridium(III) cyclometallated complexes, like other
metal complexes, present a strong oxygen quenching of their
luminescence, which is a serious drawback in most applications.
The research work presented in this thesis concerns with the
synthesis, characterization and study of the photophysical
behavior of the first caged-Iridium(III) complex (see Figure 1).
We proved that this complex shows a reduced oxygen
quenching (80%), probably caused by the shielding provided by
the ligand structure towards the excited state orbitals (see
Section 4.1).
Furthermore, three other approaches to the synthesis of
different caged-Iridium(III) complexes are reported.
The
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MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology
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MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology
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Table of Contents
Abstract ................................................................................................. iii
Table of Contents .................................................................................... v
Abbreviations ....................................................................................... viii
1.
Introduction ................................................................................... 2
1.1.
General Introduction.............................................................................................. 3
1.2.
1.2.1.
1.2.1.1.
1.2.1.2.
1.2.2.
1.2.3.
1.2.4.
1.2.5.
Quenching ............................................................................................................... 14
1.2.5.1.
1.2.5.2.
1.3.
1.3.1.
1.3.2.
1.3.3.
Applications ............................................................................................................. 21
1.3.3.1.
1.3.3.2.
1.3.3.3.
1.3.4.
1.4.
References ........................................................................................................... 25
2.
3.
3.1.
General ................................................................................................................ 31
3.2.
Materials.............................................................................................................. 32
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3.3.
Synthesis .............................................................................................................. 32
3.3.1.
Structure A .............................................................................................................. 32
3.3.2.
Structure B............................................................................................................... 36
3.3.3.
Structure C............................................................................................................... 36
3.3.4.
Structure D .............................................................................................................. 37
3.3.4.1.
3.3.4.2.
3.3.4.3.
3.3.4.4.
Tactic 1 ............................................................................................................................. 37
Tactic 2 (Failed) ................................................................................................................ 38
Reference Open Complex................................................................................................. 39
Reference Hemicaged-Complex ....................................................................................... 40
3.4.
References ........................................................................................................... 41
4.
4.1.
Structure A ........................................................................................................... 45
4.1.1.
Synthesis of Ir Caged-Complex 4 ...................................................................................... 45
4.1.1.1. Step 1. Methylation of the acid group ......................................................................... 46
4.1.1.2. Step 2. Suzuki Coupling ................................................................................................ 47
4.1.1.3. Step 3. DCC/HOBt Coupling ......................................................................................... 47
4.1.1.4. Step 4. Iridium Complexation ...................................................................................... 48
4.1.1.5. Step 5. MethylEster Deprotection and Cage Closure................................................... 49
4.1.2.
4.1.3.
Photophysics ........................................................................................................... 53
4.1.3.1.
4.1.3.2.
4.1.3.3.
4.2.
Structure B ........................................................................................................... 57
4.3.
Structure C ........................................................................................................... 59
4.4.
Structure D ........................................................................................................... 61
4.4.1.
Caged-complex ........................................................................................................ 62
4.4.2.
4.5.
References ........................................................................................................... 67
5.
Outlook ........................................................................................ 69
5.1.
Conclusions .......................................................................................................... 70
5.2.
5.3.
vi
6.
Acknowledgments ........................................................................ 72
7.
Appendix ...................................................................................... 74
7.1.
7.1.1.
7.1.2.
7.1.3.
7.1.4.
7.2.
7.2.1.
Structure A .............................................................................................................. 81
7.2.1.1.
7.2.1.2.
7.2.1.3.
7.2.1.4.
7.2.2.
Structure B............................................................................................................... 89
7.2.2.1.
7.2.3.
Structure C............................................................................................................... 91
7.2.3.1.
7.2.3.2.
7.2.3.3.
7.2.4.
Structure D .............................................................................................................. 94
7.2.4.1.
7.2.4.2.
7.2.4.3.
7.2.4.4.
7.2.4.5.
7.2.4.6.
7.2.4.7.
7.2.4.8.
7.2.4.9.
7.2.4.10.
7.2.4.11.
7.3.
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Abbreviations
DFT
ESI-MS
Density-Functional Theory
Electrospray Ionization Mass Spectrometry
fac
facial
FT-IR
HOMO
ITO
LC
LMCT
LUMO
MALDI-MS
MC
mer
MLCT
MO
OLED
RT
S0
Sn
str
T1
TLC
UV
Chemical Structures
-NPD
acac
Alq3
BCP
BHT
bpy
DCC
4,4-bis-[N-(naphthyl-N-phenylamino)biphenyl
Monoanion of acetyl acetone
tri-(8-hydroxyquinoline) aluminum(III)
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
Butylated hydroxytoluene
2,2'-bipyridine
N,N'-dicyclohexylcarbodiimede
DMA
N,N-dimethylacetamide
DMF
DMSO
dpm
HOBt
N,N-dimethylformamide
Dimethylsulfoxide
Monoanion of 2,2,6,6-tetramethyl-3,5-heptanedione
Hydroxybenzotriazole
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Lithium diisopropylamide
Lithium 2,2,6,6-tetramethylpiperidide
Monoanion of 2'-phenylpyridine
Tetrabuthyl amonium bromide
Tetrabuthyl amonium fluoride
tert-buthyldimethylsilyl
Trifluoroacetic acid
Tetrahydrofuran
Tris(2-aminoethyl)amine
C NMR
H NMR
br
COSY
d
HMBC
HMQC
m
NOE
ROESY
s
t
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