Effect of ancillary ligands on the properties of diphenylphosphoryl-substituted cationic Ir(iii) complexes

Article abstract of DOI:10.1039/C6TC04732G

A new class of diphenylphosphoryl-substituted cationic cyclometalated Ir(iii) complexes [Ir(POFdFppy)₂(N^N)]⁺PF₆^- (dFppy = 2-(2,4-difluorophenyl)pyridine) (POF1-POF6) with different N^N ancillary ligands have been synthesized and characterized. The influences of N^N ancillary ligands on the photophysical and electrochemical properties of the Ir(iii) complexes have been investigated systematically. The results demonstrate that the photoluminescence quantum yields (Φ_PL) of the complexes are dependent on the N^N ancillary ligands. POF1-POF3 equipped with phenanthroline or bipyridine ancillary ligands exhibit intense emission bands at 465-497 nm and high Φ_PL in the range of 56-61% in CH₂Cl₂. The biimidazole-type complexes POF4-POF6 exhibit an obvious substituent effect on the photophysical and electrochemical properties. Although the emission spectra of POF4 and POF5 show similar fine structures, the Φ_PL of POF5 bearing two methyl groups at the biimidazole moiety is remarkably lower (5%) than that of POF4 (45%, unmodified biimidazole). POF6 bearing two phenyl groups at the biimidazole moiety exhibits a red-shift and a weak emission band, and an extremely low Φ_PL (<3%). However, the photoluminescence quantum yields of POF5 and POF6 (35% and 41% in EC film, 40% and 65% in neat film, respectively) in the film increase effectively in comparison to those in solution. Cyclic voltammetry shows further that the structure of the ancillary ligand affects the redox properties. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed to provide insights into the electronic structures of POF1-POF6. POF1 bearing a 1,10-phenanthroline moiety demonstrates the highest oxygen sensitivity.

Full text of DOI:10.1039/C6TC04732G

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Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
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Jo uP rl ne aa sl eo df oM na ot et r ai ad l jsu sCt hme am r gi si nt rs y C
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DOI: 10.1039/C6TC04732G
Journal Name
ARTICLE
Effect of ancillary ligands on the properties of
diphenylphosphoryl‐substituted cationic Ir(III) complexes
Received 00th January 20xx,
Accepted 00th January 20xx
Hongcui Yu, Chun Liu*, Zhenni Yu, Liyan Zhang and Jinghai xiu*
+
‐
6
DOI: 10.1039/x0xx00000x
A new class of diphenylphosphoryl‐substituted cationic cyclometalated Ir(III) complexes [Ir(POFdFppy)
2
(N^N)] PF
(dFppy
=
2‐(2,4‐difluorophenyl)pyridine) (POF1‐POF6) with different N^N ancillary ligands have been synthesized and
www.rsc.org/
characterized. The influences of N^N ancillary ligands on the photophysical and electrochemical properties of the Ir(III)
complexes have been investigated systematically. The results demonstrate that the photoluminescence quantum yields
(ΦPL) of the complexes are dependent on the N^N ancillary ligands. POF1‐POF3 equipped with phenanthroline or
bipyridine ancillary ligands exhibit intense emission bands at 465‐497 nm and high ΦPL in the range of 56−61% in CH Cl
2
2
.
The biimidazole‐type complexes POF4‐POF6 exhibit an obvious substituent‐effect on the photophysical and
electrochemical properties. Although the emission spectra of POF4 and POF5 show similar fine structures, the ΦPL of
POF5 bearing two methyl groups at the biimidazole moiety is remarkably lower (5%) than that of POF4 (45%, unmodified
biimidazole). POF6 bearing two phenyl groups at the biimidazole moiety exhibits a red‐shift and weak emission band, and
an extremely low ΦPL (<3%). However, the photoluminescence quantum yields of POF5 and POF6 (35% and 41% in EC
film, 40% and 65% in neat film, respectively) in film increase effectively in comparison to those in solution. Cyclic
voltammetry shows further that the structure of the ancillary ligand affects the redox properties. Density functional theory
(DFT) and time‐dependent DFT (TD‐DFT) calculations were performed to provide insights into the electronic structures of
POF1‐POF6. POF1 bearing
a
1,10‐phenanthroline moiety demonstrates the highest oxygen sensitivity.
emission to blue region and enhance ΦPL in Ir(III) complexes,
Introduction
which are attractive for both fundamental research and
practical applications.
1
3‐19
Cyclometalated Ir(III) complexes are of special interest as
promising phosphorescent materials and have been widely
studied for their potential applications in organic light emitting
diodes (OLEDs), light‐emitting electrochemical cells (LEECs),
The diphenylphosphoryl (Ph PO) moiety with its tetrahedral
2
geometrical structure can suppress the molecular stacks and
improve the electron‐injecting and electron‐transporting
1
‐4 performances, which makes the Ph PO group widely used in
2
biological and analytical probing, photocatalysis and so on.
2
0‐22
designing new host materials.
At present, several Ir(III)
The performances of these materials in such roles depend on
their tunable emission colors and unique photoluminescence
complexes through tailoring the 2‐phenylpyridine (ppy) type
2
3‐30
5‐8
ligands with the Ph
However, blue
substituted Ir(III) complexes are rarely reported in the
2
PO moiety have been developed.
properties.
phosphorescent diphenylphosphoryl‐
Although a wide range of Ir(III) emitting materials from blue
to the near‐infrared have been reported so far, the number of
highly efficient blue phosphorescent Ir(III) complexes are
relatively limited. This is a challenging task because blue‐
emitting Ir(III) materials require a larger energy gap than
other compounds and the photoluminescence quantum yield
28
literature. In 2012, Yang and co‐workers
reported a
diphenylphosphoryl‐substituted neutral Ir(III) complex
POFIrpic, which has been successfully applied in the
construction of efficient single‐layer blue phosphorescent
2
9
OLEDs. In 2014, Yun et al.
Ir(dppfm) pic by introducing a methyl group into the 4‐position
of pyridine in POFIrpic. As a blue phosphorescent emitter,
synthesized a complex
(
Φ ) is often very low due to a significant increase in
PL
9‐11
2
nonradiative decay rates.
phosphorescent cyclometalated Ir(III) complex is iridium(III)
bis[(4,6‐difluorophenyl)‐pyridinato‐N,C ′] picolinate (FIrpic),
which has proved to be an excellent phosphorescent material
in OLEDs. Some popular strategies are adopted to tune the
The seminal sky‐blue
2
12 Ir(dppfm)
2
pic was used in OLEDs, resulting in a maximum
30
external quantum efficiency of 7.8%. Recently, Si et al.
investigated the structure‐property relationship of several
diphenylphosphoryl‐substituted cationic Ir(III) complexes with
different N^N ancillary ligands by the computational method.
Their results revealed that different ancillary ligands affected
not only the energy gap but also the ΦPL. However, to the best
of our knowledge, a systematic experimental study on the
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Linggong
Road 2, Dalian 116024, China. E‐mail: cliu@dlut.edu.cn; xiujh@dlut.edu.cn
†Electronic Supplementary Information (ESI) available: Experimental details and
characterization of products. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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effects of N^N ancillary ligands on the photophysical and
electrochemical properties of the diphenylphosphoryl‐
substituted Ir(III) complexes has not been reported.
Results and discussion
View Article Online
DOI: 10.1039/C6TC04732G
Synthesis and characterization
In this work, six diphenylphosphoryl‐substituted cationic
Chemical structures and the synthetic protocols of the cationic
cyclometalated Ir(III) complexes POF1 POF6 are shown in
Scheme 1. The ligands used in this work were synthesized
according to the reported procedures (see ESI). All of the Ir(III)
+
‐
cyclometalated Ir(III) complexes [Ir(POFdFppy)
(N^N)] PF
2 6
‐
(
POF1 POF6) were designed and synthesized with different
‐
N^N ancillary ligands. The chemical structures and
abbreviations for the N^N ancillary ligands, named phen, bpy,
dMebpy, biim, dMebiim and dPhbiim, are illustrated in Scheme
complexes were synthesized in
a
three‐step route:
cyclometalated Ir(III) μ‐chloro‐bridged dimers were first
obtained, followed by treatment with the corresponding N^N
ancillary ligand, and then a counterion exchange reaction from
1. POF1‐POF6 allow us to explore the effects of different N^N
ancillary ligands on the photophysical and electrochemical
properties of the corresponding Ir(III) complexes. In addition,
the oxygen sensitivity of these Ir(III) complexes was also
studied.
−
−
Cl to PF
6
. The corresponding characterization data for all Ir(III)
complexes are presented in the experimental section.
CH
3
N
N
N
N
N
N
N
N
NH
NH
N
N
N
N
CH
3
N
N
N
N
CH3
CH
3
phen
bpy
dMebpy
biim
dMebiim
dPhbiim
N
N
N
N
PF
6
Cl
Cl
N
N
N
(i)
(ii)
(iii)
iv)
F
O
P
F
Ir
Ir
F
F
O
P
Ir
(
F
O
P
2
O
P
2
2
F
F
F
F
POF1 N^N= phen
POF2 N^N= bpy
F
POF3 N^N= dMebpy
dFppy
POFdFppy
POF4 N^N= biim
POF5 N^N= dMebiim
POF6 N^N= dPhbiim
Scheme 1 Chemical structures of ancillary ligands and synthetic routes of Ir(III) complexes POF1‐POF6.
i) LDA, ether, ‐78 °C, N , 1.5 h; Ph PCl, overnight, RT; H , CH Cl , 3 h. (ii) IrCl ∙3H O, EtOCH CH OH/H O, 3 : 1 (v/v), 120 °C, N
N^N ancillary ligand, CH Cl /MeOH, 2 : 1 (v/v), 50°C, N , 12 h. (iv) KPF , RT, 1.5 h.
(
2
2
2
O
2
2
2
3
2
2
2
2
2
, 24 h. (iii)
2
2
2
6
Photophysical properties
UV−vis absorpꢀon spectra of POF1
‐
2 2
POF6 in CH Cl at room
temperature are presented in Fig. 1a and the corresponding
photophysical data are given in Table 1. All complexes exhibit
intense absorptions with high molar extinction coefficients (ε =
4
‐1
‐1
4
.63–7.64 × 10 M cm ) at high energy (230–260 nm), and
the biimidazole‐type complexes possess additional sharp,
intense absorptions near 286 nm. The absorption bands at
high energy are similar to those of the corresponding free
ligands (see Fig. S1, ESI) and are assigned to spin‐allowed
1
intraligand ( π−π*) transiꢀons
.
The weaker absorption bands
(
inset of Fig. 1(a)) are assigned to mixing among metal‐to‐
ligand and ligand‐to‐ligand charge transfer (MLCT/LLCT)
3
31, 32
together with ligand‐centered ( π‐π*) transitions.
POF1
exhibits the highest molar extinction coefficient, which might
be due to the larger conjugation degree of phen compared to
3
3‐35
other N^N ancillary ligands (see Fig. S1, ESI).
At room temperature, the emission spectra of POF1
CH Cl are shown in Fig. 1b. POF1 POF3 emit greenish‐blue
colors at 465‐497 nm with high Φ of 56%, 61% and 58%,
‐
POF6 in
2
2
‐
PL
+
‐
6
respectively. [Ir(POFdFppy) (phen)] PF (POF1) (λmax = 470 nm)
2
with a phen ancillary ligand emits a greenish‐blue color, which
+
‐
6
is blue‐shifted relative to [Ir(POFdFppy)
2
(bpy)] PF
(POF2)
(
2
[
λmax = 493 nm). Introducing ‐CH into the 5,5'‐position of
3
,2'‐bipyridine,
the +
emission
spectrum
465 nm)
of Fig. 1 Absorption (a) and emission (b) spectra of Ir(III) complexes POF1‐POF6 in
‐5
‐
6
2 2
CH Cl (1.0 × 10 M) at room temperature. The inset in (a) shows the magnified
Ir(POFdFppy)
2
(dMebpy)] PF
(
POF3
)
(λmax
=
spectra from 300 to 430 nm. The inset in (b) shows the emission photographs in
CH Cl (excited at 365 nm by a UV lamp).
becomes narrower and more structured compared with that of
POF2
2
2
.
2
| J. Name., 2012, 00, 1‐3
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Journal o fd oM aterials Chemr gi si nt ry C
Journal Name
ARTICLE
When
Ir(POFdFppy)
a
biim
(biim)] PF
ancillary
ligand
is
used,
View Article Online
DOI: 10.1039/C6TC04732G
+
‐
6
[
2
(
POF4) (λmax = 451 nm) shows the
most obviously blue‐shifted emission spectrum compared to
other complexes. The emission spectrum of POF4 in 2‐MeTHF
at 77K exhibits a little rigidochromic blue‐shift (5 nm)
compared with that in CH Cl at room temperature (see Fig. S3,
2
2
ESI). POF4 with a ΦPL of 45% gives a blue‐shift of
approximately 13 nm versus the emission of the
3
6
+
‐
unsubstituted complex [Ir(dFppy)
2 6
(biim)] PF (λmax = 464 nm,
ΦPL = 20% in MeOH). The results demonstrate an excellent
combination of the 2,2'‐biimidazole ancillary ligand and the
diphenylphosphoryl‐substituted cyclometalating ligand for the
construction of a blue cationic cyclometalated Ir(III) complex
Fig. 2 Emission spectra of Ir(III) complexes POF1‐POF6 in 0.5 wt% doped EC film at
room temperature. The inset shows the emission photographs in EC film (excited
at 365 nm by a UV lamp).
with a relatively high ΦPL
.
Instead of the ancillary ligand biim with dMebiim,
+
‐
[
2 6
Ir(POFdFppy) (dMebiim)] PF (POF5) (λmax = 452 nm) has
similar structured emission with POF4. When a dPhbiim is used
as the ancillary ligand, the red‐shifted emission spectrum of
+
‐
[
Ir(POFdFppy) (dPhbiim)] PF (POF6) becomes a broader and
2 6
almost unstructured shape characteristic. This may be
attributed to the different nature of the emissive excited state,
3
3
which contains much more character of MLCT/ LLCT than
those of other complexes. The assignments of the transitions
are further supported by theoretical calculations (see
theoretical calculations section). Additionally, the use of either
dMebiim or dPhbiim as the ancillary ligand induces a
significant decrease in ΦPL of the resulting Ir(III) complexes
Fig. 3 Emission spectra of Ir(III) complexes POF1‐POF6 in neat film at room
temperature. The inset shows the emission photographs in neat film (excited at
2 2
POF5 and POF6. The ΦPL of POF6 in CH Cl is extremely low
(
Table 1, ΦPL < 3%, even lower than that of POF5, ΦPL = 5%),
365 nm by a UV lamp).
which might be due to the undesired twisting of the methyl or
phenyl group on the dMebiim or dPhbiim ancillary ligand,
The emission spectra and photoluminescence quantum
37
resulting in increased nonradiative decay pathways. It is clear yields of POF1
that, introduction of the methyl or phenyl group into the 1 and were also measured. The pertinent data are summarized in
’ positions of biimidazole ligand has a negative effect on the Table 1. As shown in Fig. 2, the emission maxima of POF1
PL of the corresponding complexes POF5 and POF6 in CH Cl
POF6 in EC film are ranging from 452 to 493 nm. Their absolute
The phosphorescent lifetimes (τ) of POF1 POF4 in CH Cl
photoluminescence quantum yields in EC film are 61%, 58%,
were measured to be 2.66‐1.32 µs at room temperature (Table 64%, 45%, 35% and 41%, respectively. Compared with the
, the phosphorescence decay profiles of the Ir(III) complexes emission spectra in solutions, the emission spectra of POF2
are provided in Fig. S4, ESI). However, the τ values for POF5 and POF6 in EC film exhibit blue‐shift (see Fig. S1, ESI) due to
‐POF6 in neat and doped (0.5 wt% in EC) films
1
‐
Φ
2
2
.
‐
2
2
1
38, 39
and POF6 drop significantly (≤ 0.37 µs), which may result from the rigidochromic effect.
large nonradiative decay caused by the activated bond are in the range of 455‐510 nm for POF1
The neat film emission maxima
POF6 with absolute
‐
rotation of dMebiim and dPhbiim ancillary ligands in POF5 and photoluminescence quantum yields of 57%, 63%, 60%, 33%, 40%
POF6. Thus, the substituent effect of ancillary ligand plays an and 65%, respectively (Fig. 3 and Table 1). In neat film, the
important role in tuning the photoluminescence properties of emission spectra of all complexes except POF4 are almost
the Ir(III) complexes. The radiative decay rate (K
nonradiative decay rate (Knr) of the complexes in CH Cl
calculated (Table 1). The brightest complex POF2 has a k
r
) and identical to those in solutions (see Fig. S1, ESI). The complex
were POF4 with a biim ancillary ligand exhibits a red‐shifted
of emission
accompanied by reduced absolute
.62 × 10 s . It is notable that the large difference in Φ
photoluminescence quantum yield compared with that in EC
2
2
r
a
5
‐1
4
PL
4
0, 41
between POF4 and POF5 is owing to the distinctively different film, most probably due to intermolecular interactions.
5
‐1
nonradiative decay rate constants, knr, of 3.31 × 10 s for POF1
‐POF3 in the solid states exhibit phosphorescence
5
‐1
POF4 and 25.68 × 10 s for POF5. Due to a very low emission, behaviors similar to those in solutions, indicating that the
the data for POF6 could not be measured. It is obvious that a sterically bulky diphenylphosphoryl group might work
large k
r
and a small knr would be favorable for a high ΦPL
.
effectively in suppressing the intermolecular interactions and
excited‐state self‐quenching of the complexes from solution to
2
8, 42
solid state.
Very interestingly, POF5 and POF6 exhibit
bright light in the solid state under UV light, differing from
their weak phosphorescence in the dilute solutions. The most
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Jo uP rl ne aa sl eo df oM na ot et r ai ad l jsu sCt hme am r gi si nt rs y C
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ARTICLE
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2
O. Since POF6 is
probable reason is that the intramolecular motion is restricted with the variation of the proportion of H
in the solid state, which is considered as the main cause of insoluble in water, it could graduallyDaOgI:g1r0e.1g0a3t9e/C6uTpCo0n473th2Ge
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aggregation‐induced phosphorescent emission enhancement addition of water, showing an aggregation‐induced
4
3‐45
properties.
mixtures with different water content (0‐90%) were detected
see Fig. S6, ESI). The intensity of emission increased gradually
The emission spectra of POF6 in water/CH CN phosphorescent emission enhancement property.
3
(
Table 1 Photophysical data of POF1‐POF6.
In CH
2
Cl
2
a
b
c
d
Complex
POF1
λ
abs (nm)
λ
em (nm)
Ф
EC
Ф
neat
e
e
e
5
‐1
e
5 ‐1
Ф
solution
τ (µs)
k
r
(10 s )
k
nr (10 s )
4
70,496 (CH
470,493 (CH
467,493 (EC film)
59,479 (neat film)
93 (CH Cl
492 (CH CN)
455,479 (EC film)
92 (neat film)
65,497 (CH Cl
465,496 (CH CN)
463,491 (EC film)
68,497 (neat film)
51,479 (CH Cl
453,480 (CH CN)
452,480 (EC film)
70,482 (neat film)
52,480 (CH Cl
452,479 (CH CN)
454,478 (EC film)
55,484 (neat film)
51,512 (CH Cl
452,516 (CH CN)
453,482 (EC film)
83,510 (neat film)
2
Cl
2
)
2
32(7.28), 258(7.64),
62(0.77)
3
CN)
0.61
0.58
0.64
0.45
0.35
0.41
0.57
0.63
0.60
0.33
0.40
0.56
2.40
1.32
2.66
1.66
0.37
2.33
1.83
3
4
4
2
2
)
2
32(5.42), 256(6.86),
68(0.52)
3
POF2
POF3
POF4
POF5
POF6
0.61
0.58
0.45
0.05
4.62
2.18
2.71
1.35
f
2.95
1.58
3.31
25.68
f
3
4
4
2
2
)
2
32(4.63), 258(5.11),
62(0.36)
3
3
4
4
2
2
)
2
30(5.40), 255(6.25),
86(5.71), 362(0.59)
3
2
4
4
2
2
)
2
30(5.40), 255(6.25),
86(5.71), 362(0.59)
3
2
4
4
2
2
)
2
30(5.40), 255(6.25),
86(5.71), 362(0.59)
3
0.65
< 0.03
f
2
4
a
‐5
4
‐1
‐1
b
Measured in CH
2
Cl
2
at a concentration of 10 M and extinction coefficients (10 M cm ) are shown in parentheses. The emission maxima are the values
in bold style (λexc= 360 nm). Measured in 0.5 wt% doped EC film by the absolute method using an integrating sphere (λexc= 360 nm). Measured in neat film
c
d
e
by the absolute method using an integrating sphere (λexc= 360 nm). The quantum yields (Фsolution) in deoxygenated CH Cl were measured with
2 2
‐
1 ‐1 f
[
2 r r r
Ir(ppy) (acac)] (ФPL= 0.34) as a standard, radiative and nonradiative decay rates of k and knr were calculated from k = ФPL × τ , knr = τ ‐ k . Data not was
not measured due to a very low emission. All measured at ambient temperature.
bipyridine. Additionally, POF4 and POF5 have similar redox
potentials and exhibit larger redox gaps than others. The redox
potential of POF6 is affected by the dPhbiim ancillary ligand,
and POF6 has a lower redox gap than that of POF4. Thus, it is
clear that the structure of the ancillary ligand affects the
electrochemical properties of the corresponding Ir(III)
complexes.
The measured onset oxidation and reduction potentials of
each Ir(III) complex were used to calculate the HOMO and
LUMO levels, respectively. As listed in Table 2, the energy gaps
Electrochemical Properties
The electrochemical properties of POF1
by cyclic voltammetry (CV) in CH Cl (the cyclic voltamograms
‐POF6 were measured
2
2
of POF1
presented in Table 2. The CVs of POF1
onset oxidation potentials at approximately 1.87 V and they
are more anodic than those of POF4 POF6 (1.68, 1.64, and
.58 V, respectively). POF1 and POF2 show much less negative
‐
POF6 see Fig. S4, ESI) and the corresponding data are
‐
POF3 display similar
‐
1
onset reduction potentials (‐1.25 V for POF1 and ‐1.22 V for
POF2), which indicates their lower LUMO energy levels.
Introducing the methyl substituent at the 5,5'‐position of 2,2'‐
bipyridine for POF3 makes the reduction process shift to a
(
Eg) between the HOMO and LUMO levels of POF1
‐POF6 are
3
.12, 3.10, 3.23, 3.53, 3.52 and 3.30 eV, respectively, which
agree well with the observed greenish‐blue to blue emission
spectra of these complexes.
more cathodic potential at ‐1.38 V
complexes POF4 POF6 show more negative reduction
potentials relative to POF1 POF3 because the biimidazole
moiety is more electron‐rich than phenanthroline and
. The biimidazole‐type
‐
‐
4
| J. Name., 2012, 00, 1‐3
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Jo uP rl ne aa sl eo df oM na ot et r ai ad l jsu sCt hme am r gi si nt rs y C
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Table 2 Electrochemical data of POF1
‐
POF6
.
reduction potential measured by CV (‐1.38 V, Table 2). The
replacement of the phen‐ or bpy‐type ligand by a biimidazole‐
type ligand results in destabilization of both the HOMO and
LUMO energies with a increase in the overall energy gap,
which is also supported by experimental results (Table 2).
View Article Online
DOI: 10.1039/C6TC04732G
࢕
࢕
࢚ࢋ࢙࢔a
࢚ࢋ࢙࢔࢕a
ࢊࢋ࢘
b
c
c
ࡱ
ࡱ
E
g
HOMO
[eV]
LUMO
[eV]
࢞
Complex
[
V]
[V]
[eV]
POF1
POF2
POF3
POF4
POF5
POF6
1.87
1.88
1.85
1.68
1.64
‐1.25
‐1.22
‐1.38
‐1.85
‐1.88
‐1.72
3.12
3.10
3.23
3.53
3.52
3.30
‐6.27
‐6.28
‐6.25
‐6.08
‐6.04
‐5.98
‐3.15
‐3.18
‐3.02
‐2.55
‐2.52
‐2.68
Different from POF1‐POF3, the HOMOs of POF4‐POF6 are
predominantly at the ppy of the cyclometalating ligand,
iridium atom and biimidazole moieties of ancillary ligand. The
LUMOs of POF4 and POF5 are mainly localized on the ppy of
cyclometalating ligand and biimidazole of ancillary ligand.
Substitution of 2,2'‐biimidazole by ‐CH the complex POF5
3
shows nearly the same LUMO and HOMO levels relative to
POF4 (Fig. 4), in accord with the experimental results (Table 2).
However, the LUMO of POF6 is mainly localized at the
biimidazole moieties of ancillary ligand, and also partially at
the phenyl rings of the ancillary ligand. Compared with POF4
and POF5, there is a decrease in the HOMO‐LUMO energy gap
for POF6, which is in good agreement with the experimental
results (Table 2).
1.58
a
−1
0
.1 M [Bu
4
N]PF
6
2 2
in CH Cl , scan rate 100 mV s , measured using saturated
b c
calomel electrode (SCE) as the standard.
g
E = ELUMO ‐ EHOMO. EHOMO(eV) = ‐
௢
௡௦௘௧
௢௡௦௘௧
e(4.4 +ܧ௢௫ ), ELUMO(eV)= ‐e(4.4 +ܧ௥௘ௗ ), HOMO and LUMO denote highest‐
occupied molecular orbital and lowest‐unoccupied molecular orbital,
respectively.
Theoretical calculations
The vertical excitation energies and molecular orbitals
involved in the excitations for the lowest energy triplet state
The electronic structures of POF1
density functional theory (DFT) and time‐dependent DFT (TD‐
DFT) calculations. As shown in Fig. 4, POF1 POF3 present
similar molecular orbital topologies, the HOMOs of POF1
POF3 reside on the iridium center and ppy of the
cyclometalating ligands, while the LUMOs reside on the
ancillary ligands. The LUMOs appear at similar energies for
POF1 (‐2.80 eV) and POF2 (‐2.84 eV), justifying the almost
identical values recorded for the reduction potential of both
complexes (‐1.25 and ‐1.22 V, Table 2). The LUMO of POF3 (‐
‐POF6 were investigated by
(
T1) are summarized in Table 3 (Electron density maps of the
‐
frontier molecular orbital of POF1‐POF6 at the ground state
‐
optimized geometries, see Fig. S7, ESI). Besides the
3
3
predominant characters of MLCT and LLCT, the T states of
1
3
POF1
‐POF3 have different degrees of LC character. POF4 and
POF5 have the predominant LC nature of the T
3
1
state, which
explains the fine structures of emission spectra. However, the
emitting excited state of POF6 involves much more
3
3
MLCT/ LLCT character, which can explain its broad
unstructured emission band.
2
.72 eV) is slightly destabilized by the electron‐donating effect
of the ‐CH3 substituent in accord with a more cathodic
-
1.0
1.5
2.0
2.5
3.0
-
-
-
2.09
-2.07
4.27
-
2.19
-
LUMO
HOMO
-
2.72
6.48
4.28
-
2.80
-2.84
4.16
-
3
.70
3.66
-6.51
3.76
-6.34
-6.35
-6.37
-
-6.50
-6.5
-7.0
-7.5
POF1
POF2
POF3
POF4
POF5
POF6
Fig. 4 Calculated frontier molecular orbital energy levels together with the electron density distributions for POF1‐POF6.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 5
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Jo uP rl ne aa sl eo df oM na ot et r ai ad l jsu sCt hme am r gi si nt rs y C
Page 6 of 10
ARTICLE
Journal Name
Table 3 Calculated triplet states of POF1‐POF6 by a TD‐DFT approach.
View Article Online
a
b
c
DOI: 10.1039/C6TC04732G
Complex State
E
(eV) Composition
CI
Character
H‐13
→
L+1
0.3233
LC
POF1
POF2
POF3
POF4
POF5
POF6
T
1
T
1
T
1
T
1
T
1
T
1
2.83
H‐4
→
L+1
0.2735 LC/MLCT/LLCT
H
→
L
0.2323
MLCT/LLCT
H
→
L
0.5663
0.1989
0.1556
MLCT/LLCT
LC
2.81
2.83
2.95
2.92
2.87
H‐14
H‐1
→
L
L
→
L
MLCT/LLCT
H
→
L
0.3972
0.3639
MLCT/LLCT
LC
H‐13
H‐4
→
Fig. 5 Stern‐Volmer plots for oxygen sensing films of POF1‐POF6 (0.5 wt%)
immobilized in EC (intensity ratios I /I versus O partial pressure).
0 2
→
L
0.3335 LC/MLCT/LLCT
H
→
L
0.4624
0.2282
0.2071
LC
H‐4
→
L
LC/LLCT
LC/MLCT
H
→L+1
H‐2
→
L+1
0.4958
LC
H
→
L+1
0.3593 LC/MLCT/LLCT
H‐2
→
L
L
0.2185
LC/LLCT
H‐2
→
0.5310
0.3804
0.1757
LC/MLCT
MLCT/LLCT
LLCT
H
→L
H‐3
→
L
a
b
Only the selected low‐lying excited states are presented. Only the main
configurations are presented. and denote HOMO and LUMO,
respectively. The Configuration‐interaction (CI) coefficients are in absolute Fig. 6 Response time and reversibility of POF1 (0.5 wt%) immobilized in EC when
H
L
C
values. Oscillator strengths are zero because of the neglect of spin‐orbit
coupling in the TD‐DFT calculations.
2 2
cycling from 100% N to 100% O atmosphere.
0
The I /I100 values of these Ir(III) complexes immobilized in EC
Oxygen sensitivity properties
films are 7.7, 2.8, 5.2, 5.0, 2.0 and 3.6 respectively. Stern‐
Volmer plots are shown in Fig. 5. POF1 bearing a phen ancillary
ligand supported in EC exhibits the highest oxygen sensitivity.
The oxygen sensing film of POF1 demonstrates good
reproducibility while oxygenated and deoxygenated gases
were switched for 4000 s (Fig. 6). Additionally, fast response
time (ca. 5.8 s for switching from N to O ) and recovery time
Cyclometalated Ir(III) complexes are an important class of
46
probes for oxygen sensing. A new family of cyclometalated
Ir(III) complexes with good oxygen sensing properties have
47‐50
been reported.
sensitive probes
So far, many cyclometalated Ir(III) oxygen‐
(OSPs) used for oxygen sensing are orange or
2
2
green emitters, while greenish‐blue to blue phosphorescent
1
6
(ca. 7.2 s for switching from O to N ) were obtained. Other
2 2
Ir(III) complexes as the OSPs are rarely reported. Therefore, it
is attractive for developing blue OSPs, which may provide a
possibility to improve the efficiency of the sensors in the entire
region of the visible spectrum. In this study, the oxygen
Ir(III) complexes relatively less sensitive to quenching by O can
2
be envisioned for some systems such as water splitting and
OLED display.
sensitivity of POF1‐POF6 as greenish‐blue to blue Ir(III)
emitters were evaluated. The ethylcellulose (EC) with a high
oxygen permeability coefficient was used to immobilize the
Conclusions
5
1
In summary, a series of new diphenylphosphoryl‐substituted
cationic
Ir(III) complexes and the corresponding data were fitted by a
52‐54
cyclometalated
Ir(III)
complexes
two‐site model (Table S1, ESI)
0 100 0 100
. The I /I ratio (I and I
+
‐
[
Ir(POFdFppy) (N^N)] PF with different N^N ancillary ligands
represent the detected phosphorescent intensities from a film
exposed to 100% N and 100% O , respectively) can be used to
2
6
have been designed and synthesized. Both of experimental
and theoretical results demonstrate that the structures of
ancillary ligands strongly affect the photophysical and
electrochemical properties of the corresponding Ir(III)
complexes. In this study, all Ir(III) complexes show emission
from the greenish‐blue to blue at room temperature. The
electron‐rich 2,2'‐biimidazole (biim) ancillary ligand is found to
be the most useful one for constructing a blue Ir(III) complex
POF4, compared with phen‐ and bpy‐type Ir(III) complexes
2
2
evaluate the oxygen sensitivity.
POF1‐POF3. The complexes POF1‐POF4 show high ΦPL both in
6
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
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Jo uP rl ne aa sl eo df oM na ot et r ai ad l jsu sCt hme am r gi si nt rs y C
Journal Name
ARTICLE
solution and in solid state. In contrast to POF4
with the electron‐donating substituents of methyl or phenyl at refluxed at 120 °C under nitrogen for 24DOhI.: 1A0f.1t0e3r9c/Co6oTlCin0g4,73th2Ge
the biim ancillary ligand show a significant decrease in Φ in solid precipitate was collected washed with water and EtOH.
CH Cl . POF5 and POF6 exhibit much higher Φ in solid state Without any further purification, the dimeric Ir(III) complex
, POF5 and POF6 in a mixture of 2‐ethoxyethanol (15 mL) and wateVriew(5ArmticlLe)Oanlninde
PL
,
2
2
PL
than those in solution. Electrochemical measurements showed reacted with 3.0 equiv. desired ancillary ligand in a mixture of
that the redox potentials of phen‐ and bpy‐type complexes dichloromethane (10 mL) and methanol (5 mL) at 50 °C under
POF1
‐
POF3 are shifted anodically compared to those of the nitrogen for 12 h. The reaction mixture was cooled to room
POF6. When immobilized in temperature and an aqueous solution of KPF was added to
biimidazole‐type complexes POF4
‐
6
ethyl cellulose film, POF1 bearing a phen ancillary ligand afford the crude product. The resulting solid was filtered,
exhibits the highest oxygen sensitivity. The above results show further purified by column chromatography over silica using
clearly that it is possible to tune the emission color, ΦPL and CH Cl : petroleum ether (1:1) as eluent to provide the desired
2
2
oxygen sensitivity properties of the Ir(III) complexes by the Ir(III) complexes.
1
N^N ancillary ligands.
6
POF1: Yield 52%, yellow solid; H NMR (400 MHz, DMSO‐d ) δ
8
.97 (d, J = 8.3 Hz, 2H), 8.42 (s, 2H), 8.38 – 8.33 (m, 2H), 8.12
dd, J = 8.3, 5.1 Hz, 2H), 8.06 (d, J = 8.8 Hz, 2H), 7.89 (t, J = 8.2
Hz, 2H), 7.83 – 7.75 (m, 8H), 7.63 – 7.52 (m, 14H), 7.06 (t, J =
(
Experimental
1
3
6
.7 Hz, 2H), 5.82 (dd, J = 9.6, 3.6 Hz, 2H). C NMR (100 MHz,
Materials and instruments
DMSO‐d ) δ 163.7, 161.8, 161.5, 161.0, 159.7, 151.4, 150.1,
6
All starting materials were purchased from commercial 145.5, 140.3, 139.6, 134.4, 133.5, 131.9, 131.3, 130.6, 129.3,
1
suppliers and used without further purification. H NMR and 128.7, 128.4, 127.5, 125.0, 124.0, 114.9, 104.9, 104.1. HRMS
13
+
C NMR spectra were recorded on a 400 MHz Varian Unity (MALDI‐TOF, m/z): calcd for C H F N O P Ir [M – PF ]
5
8
38
4
4
2
2
6
Inova spectrophotometer. Mass spectra were recorded with a 1153.2035, found 1153.2028; calcd for C H F N O P Ir [M –
4
6
30
4
2
2 2
+
MALDI micro MX spectrometer. Elemental analyses for C, H, PF – phen] 973.1348, found 973.1061. Elem. anal. calcd (%)
6
and N were performed on an Elementar‐vario EL III elemental for C H F IrN O P : C, 53.67; H, 2.95; N, 4.32. Found: C,
5
8
38 10
4
2 3
analyzer. UV-Vis absorption spectra were recorded on a 53.50; H, 3.02; N, 4.34.
Lambda 750s spectrophotometer. Emission spectra were POF2: Yield 59%, yellow solid; H NMR (400 MHz, DMSO‐d ) δ
1
6
recorded with a HITACHI F‐7000 spectrofluorimeter (λ = 360 8.91 (d, J = 8.2 Hz, 2H), 8.39 – 8.31 (m, 2H), 8.07 (d, J = 8.7 Hz,
exc
nm). Phosphorescence lifetimes were measured on an 2H), 7.99 – 7.93 (m, 4H), 7.81 – 7.70 (m, 12H), 7.64 – 7.50 (m,
Edinburgh FLS920 spectrometer. An Oxford OptistatDN‐V 12H), 7.24 (t, J = 6.7 Hz, 2H), 5.72 (dd, J = 9.6, 3.3 Hz, 2H). 13
C
cryostat instrument equipped with an intelligent temperature NMR (100 MHz, DMSO‐d ) δ 163.7, 162.3, 161.8, 161.5, 159.7,
6
controller and liquid nitrogen was used for data recorded at 77 154.9, 150.4, 149.9, 140.5, 134.4, 133.5, 131.9, 130.6, 130.5,
K. Photoluminescence quantum yields (Φ ) were measured 129.3, 129.0, 128.7, 128.6, 125.4, 124.1, 114.8, 104.8, 104.1.
PL
+
relative to [Ir(ppy) (acac)] (Ф = 0.34 in CH Cl , under HRMS (MALDI‐TOF, m/z): calcd for C H F N O P Ir [M – PF ]
2
PL
2
2
56 38
4
4
2
2
6
deoxygenated conditions). Solid state ΦPL values were 1129.2035, found 1129.2035; calcd for C H F N O P Ir [M –
46
30
4
2
2 2
+
measured using an absolute PL quantum yield measurement PF – bpy] 973.1348, found 973.1182. Elem. anal. calcd (%)
6
system (C11347‐11, Hamamatsu Photonics K.K.). Cyclic for C H F IrN O P : C, 52.79; H, 3.01; N, 4.40. Found: C,
5
6
38 10
4
2 3
voltammograms of the Ir(III) complexes were recorded on an 52.83; H, 3.38; N, 4.39.
1
electrochemical workstation (BAS100B/W, USA) at room POF3: Yield 56%, yellow‐green solid; H NMR (400 MHz,
temperature in a 0.1 M [Bu N]PF solution under argon DMSO‐d ) δ 8.73 (d, J = 8.4 Hz, 2H), 8.15 (d, J = 7.5 Hz, 2H),
4
6
6
conditions. Phosphorescent intensity response of sensing films 8.09 (d, J = 8.7 Hz, 2H), 7.96 (t, J = 7.7 Hz, 2H), 7.79 – 7.69 (m,
of the Ir(III) complexes were recorded with a F‐7000 10H), 7.65 – 7.58 (m, 6H), 7.57 – 7.50 (m, 8H), 7.24 (t, J = 6.6
13
spectrofluorimeter. The structures of the Ir(III) complexes Hz, 2H), 5.74 – 5.70 (m, 2H), 2.35 (s, 6H). C NMR (100 MHz,
were optimized using density functional theory (DFT) with the DMSO‐d ) δ 163.6, 161.8, 161.5, 159.7, 152.6, 149.9, 140.9,
6
B3LYP functional and 6‐31G(d)/LanL2DZ basis set. The LanL2DZ 140.3, 139.2, 134.3, 133.4, 132.0, 129.0, 128.7, 128.6, 125.1,
basis set was used to treat the iridium atom, whereas the 6‐ 124.3, 124.2, 124.0, 114.9, 104.6, 103.8, 18.2. HRMS (MALDI‐
+
3
1G(d) basis set was used to treat all other atoms. All TOF, m/z): calcd for C H F N O P Ir [M – PF ] 1157.2348,
5
8
42
4
4
2
2
6
calculations were performed with the Gaussian 09 software found 1157.2363; calcd for C H F N O P Ir [M – PF
–
4
6
30
4
2
2
2
6
55
+
package. CH Cl was used as the solvent for the calculations dMebpy] 973.1348, found 973.0884. Elem. anal. calcd (%) for
2
2
(CPCM model).
C H F IrN O P : C, 53.50; H, 3.25; N, 4.30. Found: C, 52.90; H,
58 42 10 4 2 3
3
.24; N, 4.36.
Synthesis
1
POF4: Yield 45%, lime green; H NMR (400 MHz, DMSO‐d
6
) δ
Synthesis of C^N cyclometalating ligand and N^N ancillary 8.01 (d, J = 8.6 Hz, 2H), 7.93 (t, J = 7.6 Hz, 2H), 7.78 – 7.71 (m,
ligands. The different C^N cyclometalating ligand and N^N 10H), 7.60 – 7.49 (m, 14H), 7.30 (t, J = 6.6 Hz, 2H), 6.68 (s, 2H),
13
ancillary ligands were synthesized by previously reported 5.79 (dd, J = 9.8, 3.7 Hz, 2H). C NMR (100 MHz, DMSO‐d ) δ
6
method (see ESI).
163.4, 162.4, 161.9, 161.4, 159.4, 149.5, 140.9, 139.5, 134.5,
Synthesis of the Ir(III) complexes POF1‐POF6. IrCl
3
∙3H
2
O (0.5 133.5, 131.9, 130.5, 130.4, 129.5, 128.7, 128.6, 126.6, 124.5,
mmol) and 2.5 equiv. of cyclometalating ligand were dissolved 123.4, 122.4, 114.9, 103.6, 102.8. HRMS (MALDI‐TOF, m/z):
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 7
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Jo uP rl ne aa sl eo df oM na ot et r ai ad l jsu sCt hme am r gi si nt rs y C
Page 8 of 10
ARTICLE
Journal Name
1107.1940, found 9 Y. You and S. Y. Park, Dalton Trans., 2009, 8, 1267‐1282.
+
36 4 6 2 2 6
calcd for C52H F N O P Ir [M – PF ]
View Article Online
+
1
1
1
0 Y. Chi and P. Chou, Chem. Soc. Rev., 2010D, O39I:,1603.180.39/C6TC04732G
1
9
107.1923; calcd for C H F N O P Ir [M – PF –biim]
46 30 4 2 2 2 6
73.1348, found 973.1491. Elem. anal. calcd (%) for
1 C. L. Ho and W. Y. Wong, New J. Chem., 2013, 37, 1665‐1683.
2 C. Adachi, R. C. Kwong, P. Djurovich, V. Adamovich, M. A. Baldo,
M. E. Thompson and S. R. Forrest, Appl. Phys. Lett., 2001, 79,
C H F IrN O P : C, 49.89; H, 2.90; N, 6.71. Found: C, 49.57; H,
5
2
36 10
6
2 3
3
.31; N, 7.13.
2
082‐2084.
1
POF5: Yield 41%, lime green; H NMR (400 MHz, DMSO‐d
6
) δ
.02 (d, J = 8.6 Hz, 2H), 7.95 (t, J = 8.1 Hz, 2H), 7.80 – 7.69 (m,
0H), 7.62 – 7.48 (m, 14H), 7.32 (t, J = 6.6 Hz, 2H), 6.64 (d, J =
1
3 C. F. Chang, Y. M. Cheng, Y. Chi, Y. C. Chiu, C. C. Lin, G. H. Lee, P.
T. Chou, C. C. Chen, C. H. Chang and C. C. Wu, Angew. Chem., Int.
Ed., 2008, 47, 4542‐4545.
8
1
1
1
3
.1 Hz, 2H), 5.73 (dd, J = 9.8, 3.6 Hz, 2H), 4.23 (s, 6H). C NMR
14 Y. Chiu, Y. Chi, J. Hung, Y. Cheng, Y. Yu, M. Chung, G. Lee, P. Chou,
C. Chen and C. Wu, ACS Appl. Mater. Interfaces, 2009, 1, 433.
(
100 MHz, DMSO‐d ) δ 163.3, 162.2, 161.6, 159.5, 149.7, 140.7,
6
1
1
(
39.7, 134.5, 133.7, 131.8, 130.5, 130.4, 129.4, 128.7, 128.6, 15 J. B. Kim, S. H. Han, K. Yang, S. K. Kwon, J. J. Kim and Y. H. Kim,
28.0, 126.7, 124.6, 123.4, 114.9, 103.8, 103.0, 37.9. HRMS
Chem. Commun., 2015, 51, 58‐61.
+
1
6 M. Marín‐Suárez, B. F. E. Curchod, I. Tavernelli, U. Rothlisberger,
R. Scopelliti, I. Jung, D. D. Censo, M. Grätzel and A. Fernández‐
Gutiérrez, Chem. Mater., 2012, 24, 2330‐2338.
7 S. Lee, S. O. Kim, H. Shin, H. J. Yun, K. Yang, S. K. Kwon, J. J. Kim
and Y. H. Kim, J. Am. Chem. Soc., 2013, 135, 14321‐14328.
8 T. Kim, J. Lee, U. L. Sang and H. L. Min, Organometallics, 2015, 34,
MALDI‐TOF, m/z): calcd for C H F N O P Ir [M – PF ]
54 40 4 6 2 2 6
1
135.2253, found 1135.2231; calcd for C H F N O P Ir [M –
46 30 4 2 2 2
+
PF – dMebiim] 973.1348, found 973.1061. Elem. anal. calcd
6
1
(
5
%) for C H F IrN O P : C, 50.67; H, 3.15; N, 6.57. Found: C,
54 40 10 6 2 3
0.97; H, 3.10; N, 6.37.
POF6: Yield 38%, green‐yellow solid; H NMR (400 MHz, DMSO‐
1
1
3455‐3458.
d6) δ 8.27 (d, J = 5.7 Hz, 2H), 8.07 (d, J = 8.7 Hz, 2H), 7.99 (t, J =
19 D. Ma, L. Duan, Y. Wei, L. He, L. Wang and Y. Qiu, Chem.
Commun., 2014, 50, 530‐532.
.49 (m, 8H), 7.37 (t, J = 6.7 Hz, 2H), 7.22 – 7.08 (m, 10H), 6.98 20 F. Hsu, C. Chien, C. Shu, C. Lai, C. Hsieh, K. Wang and P. Chou,
7
7
(
.9 Hz, 2H), 7.82 – 7.72 (m, 10H), 7.65 – 7.57 (m, 4H), 7.56 –
1
3
s, 2H), 5.81 (dd, J = 9.7, 3.0 Hz, 2H). C NMR (100 MHz,
Adv. Funct. Mater., 2009, 19, 2834‐2843.
DMSO‐d ) δ 163.4, 162.1, 161.6, 161.3, 160.4, 159.5, 150.4, 21 S. O. Jeon and J. Y. Lee, J. Mater. Chem., 2012, 22, 4233‐4243.
6
2
2
2
2
2
2
2
2
3
2 X. Yang, G. Zhou and W. Y. Wong, Chem. Soc. Rev., 2015, 44,
1
1
1
–
40.0, 138.8, 135.7, 134.6, 133.8, 131.8, 130.6, 130.5, 129.6,
29.3, 128.7, 128.6, 128.1, 124.9, 124.6, 123.5, 115.2, 104.2,
03.4. HRMS (MALDI‐TOF, m/z): calcd for C H F N O P Ir [M
8484‐8575.
3 G. Zhou, C. L. Ho, W. Y. Wong, Q. Wang, D. Ma, L. Wang, Z. Lin, T.
B. Marder and A. Beeby, Adv. Funct. Mater., 2008, 18, 499‐511.
4 G. Zhou, C. Ho, W. Wong, D. Ma, L. Wang and Z. Lin, Chem. ‐
Asian J., 2008, 3, 1830‐1841.
46
30
4
2
2 2
+
PF – dPhbiim] 973.1348; found 973.2037. Elem. anal. calcd
6
(%) for C H F IrN O P : C, 54.74; H, 3.16; N, 5.98. Found: C,
64 44 10 6 2 3
5
4.33; H, 3.37; N, 5.64.
5 L. Deng, T. Zhang, R. Wang and J. Li, J. Mater. Chem., 2012, 22,
15910‐15918.
6 M. Zhu, Y. Li, J. Miao, B. Jiang, C. Yang, H. Wu, J. Qin and Y. Cao,
Org. Electron., 2014, 15, 1598‐1606.
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Acknowledgements
The authors thank the financial support from the National
Natural Science Foundation of China (21276043, 21421005),
Dalian University of Technology (DUT, SYSWX201507), and
Open Fund of Key Laboratory of Biotechnology and
Bioresources Utilization (Dalian Minzu University, KF2015002),
State Ethnic Affairs Commission & Ministry of Education. We
thank Prof. Jiuyan Li and Prof. Jiangli Fan at DUT, for valuable
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Journal of Materials Chemistry C
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View Article Online
DOI: 10.1039/C6TC04732G
Effect
of
ancillary
ligands
on
the
properties
of
diphenylphosphoryl-substituted cationic Ir(III) complexes
Hongcui Yu, Chun Liu*, Zhenni Yu, Liyan Zhang and Jinghai Xiu*
[
*]Corresponding Author
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Linggong Road 2, Dalian
16024, China.
1
Tel.: +86-411-84986182.
E-mails: cliu@dlut.edu.cn; xiujh@dlut.edu.cn
A new class of greenish-blue to blue emitting diphenylphosphoryl-substituted
cationic cyclometalated Ir(III) complexes (POF1-POF6) with different N^N ancillary
ligands are reported.