Using phosphorescent PtAu3 clusters for superior solution-processable organic light emitting diodes with very small efficiency roll-off

Article abstract of DOI:10.1039/c8tc03270j

A family of highly phosphorescent PtM₃ (M = Au, Ag) aromatic acetylide cluster complexes supported with tetraphosphine and stabilized by μ-chloride were synthesized by the use of weakly luminescent mononuclear Pt(PPh₃)₂(CCR)₂ (R = aryl) as precursors. The formation of PtM₃ cluster complexes involves the abstraction of chloride from dichloromethane. The dramatic difference between PtAg₃ and PtAu₃ cluster structures arises from the location of the Pt atom, which is at the center of the triangle-planar PtM₃ cluster for M = Ag whereas at one of the three corners in the PtM₃ triangle plane for M = Au. Perturbation of the chloride ion in complexation by using a halide-abstracting agent results in the formation of PtM₂ heterotrinuclear structures as demonstrated by X-ray crystallography. The PtAu₃ complexes display intense phosphorescence with quantum yields of over 90% in doped films. High-efficiency OLEDs based on PtAu₃ complexes were attained with an external quantum efficiency (EQE) over 18%. Most importantly, the optimized devices exhibit extremely small efficiency roll-off (less than 1%) at a practical brightness over 1000 cd m^-2, which is one of the best performances for solution-processable phosphorescent OLEDs.

Full text of DOI:10.1039/c8tc03270j

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ISSN 2050-7526
PAPER
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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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DOI: 10.1039/C8TC03270J
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ARTICLE
Using Phosphorescent PtAu3 Clusters for Superior Solution-
Processable Organic Light Emitting Diodes with Very Small
Efficiency Roll-Off
Received 00th January 20xx,
Accepted 00th January 20xx
Nagarajan Natarajan, Lin-Xi Shi, Hui Xiao, Jin-Yun Wang, Li-Yi Zhang, Xu Zhang,* Zhong-Ning Chen*
DOI: 10.1039/x0xx00000x
A family of highly phosphorescent PtM3 (M = Au, Ag) aromatic acetylide cluster complexes supported with tetraphosphine
and stabilized by ꢀ-chloride were synthesized by the use of weakly luminescent mononuclear Pt(PPh3)2(C≡CR)2 (R = aryl) as
precursors. The formation of PtM3 cluster complexes involves the abstraction of chloride from dichloromethane. The
dramatic difference between PtAg3 and PtAu3 cluster structures arises from the location of Pt atom, which is at the center
of triangle-planar PtM3 cluster for M = Ag whereas at one of the three corners in the PtM3 triangle plane for M = Au.
Perturbation of chloride ion in complexation by using halide-abstracting agent results in the formation of PtM2
heterotrinuclear structures as demonstrated by X-ray crystallography. The PtAu3 complexes display intense
phosphorescence with quantum yields over 90% in doped films. High-efficiency OLEDs based on PtAu3 complexes were
attained with external quantum efficiency (EQE) over 18%. Most importantly, the optimized devices exhibit extremely
small efficiency roll-off (less than 1%) at a practical brightness over 1000 cd m-2, which is one of the best performances for
solution-processable phosphorescent OLEDs.
www.rsc.org/
mild preparative condition, high luminescent quantum yield,
good resistant to thermal and chemical degradation, and
favorable solubility in organic solvents, making them as
Introduction
Highly phosphorescent metal complexes continue to receive a
great deal of attention because of their useful photophysical
properties that lead to develop high-efficiency organic light
emitting diodes (OLEDs).1 Notably, most of highly efficient
phosphorescent emitters reported so far suffer from severe
efficiency roll-off at high current density or practical luminance
over 1000 cd m-2, which is the main hurdle to satisfy stable
high-performance OLEDs. The efficiency roll-off stems mainly
from long excited-state lifetimes of the emitters leading to
excellent candidates for efficient solution-processable OLEDs.9-
21
Except for the lower volatility, phosphorescent polynuclear
metal cluster complexes display several advantages over
mononuclear complexes, such as (i) better molecular rigidity
due to the formation of polynuclear aggregates and thus more
intense phosphorescence, (ii) more convenience for the
regulation of emissive energy and colors by modifying both
bridging and ancillary ligands, and (iii) more diverse
phosphorescent characteristics owing to the participation of
multiple metal ions and the formation of intermetallic
interaction.
triplet
− triplet annihilation (TTA) and triplet–charge
annihilation (TCA).2 Several strategies have been proposed to
overcome this issue, including the design of emitters with
short-lived triplet excited state,3 broadening the
recombination zone,4 doping the emitters with large
dendrons,5 reducing intermolecular aggregation, and
developing bipolar host materials.6-8 Undoubtedly, more
design strategies to attain a small efficiency roll-off remain to
be established.
Many square-planar mononuclear platinum(II) complexes
are non-luminescent or weakly emissive at room temperature,
−
but their corresponding PtII MI (M = Ag, Au) heteronuclear
cluster complexes become highly phosphorescent because of
the much enhanced molecular rigidity upon the formation of
aggregate structures.20-26 For instance, mononuclear
precursors Pt(PPh3)2(C
luminescent at ambient temperature, but intense
phosphorescence is frequently achieved when
Pt(PPh3)2(C
CR)2 react with M+ and PhP(CH2PPh2)2 (dpmp) or
(Ph2PCH2PCH2-)2 (dpmppe) to produce PtM2 heterotrinuclear
entities through the substitution of PPh3.20-22 The PtII MI
≡CR)2 (R = alkyl or aryl) are weakly
Among various available phosphorescent emitters, metal
cluster complexes are of particular interest because of their
≡
−
intermetallic interactions play a crucial role in determining
phosphorescent characteristics as well as improving molecular
rigidity to achieve highly efficient phosphorescence in these
PtM2 complexes.
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Synthesis and Characterization
The preparation of PtM3 heterotetranuclear cluster complexes
(Scheme 1) was carried out using the branched C3 symmetrical
tris(diphenylphosphinomethyl)phosphine (tdpmp) as the
supporting ligand. Thus, the reactions of Pt(PPh3)2(C
tdpmp and Ag(tht)ClO4 in 1 : 2 : 3 molar ratio expectedly gave
PtAg3 heterometallic cluster complexes . The products
≡CR)2,
1−5
were then purified by chromatography on silica gel columns
using CH2Cl2-MeOH (v/v = 20 : 1) as the eluent to give pure
solids in good yields (72−84%). These compounds were
1
satisfactorily characterized by HRMS (ESI), H and 31P[1H] NMR
spectroscopy. Initially, the peaks observed from the 31P[1H]
NMR spectrum of PtAg3 complex
1 (Figure 1a) were somewhat
puzzling. We expected two sets of peaks corresponding to the
P atoms bound to Pt and Ag centers, respectively. But we
observed three sets of signals centered at 18.0 to 19.3 ppm,
9.0 to 9.6 ppm, and
−0.6 to −4.0 ppm in 1 : 1 : 2 ratio,
corresponding to 2P, 2P and 4P donors, respectively. The first
multiplets with satellite peaks (Figure 1a, signal a) arise from
the central P donor of P(CH2PPh2)3 bonded to the Pt(II) center.
The third set of signals (Figure 1a, signal c) is ascribed to two
terminal P donors bound to two Ag(I) centers bridged by ꢀ-Cl
atom, whereas the second group of signals (Figure 1a, signal b)
is due to the third terminal P donor bound to another Ag(I)
center. The occurrence of two groups of phosphorus signals
for each equivalent P atom arises from fluxional structures of
PtAg3 complexes due to the labile Ag−Cacetylide or/and Ag−Cl
bonds in fluid solutions as demonstrated previously.21a,23,27
Scheme 1 Synthetic Route to PtM3 and PtM2 (M = Ag or Au) Complexes.
Since tetraphosphine P(CH2PPh2)3 (tdpmp) as a bulkier
supporting ligand than triphosphine PhP(CH2PPh2)2 (dpmp)
could afford Pt−M cluster aggregates with higher nuclearity,
better molecular rigidity and larger steric effect, it is likely that
the efficiency roll-off in devices can be more effectively
restrained because of the much reduced intermolecular
aggregation. As expected, high-efficiency solution-processed
OLEDs based on tetraphosphine-supported PtAu3 cluster
complexes were successfully achieved with the peak CE of 62.8
1
cd A− and EQE of 18.1%. The devices display extremely low
Fig 1 The 31P[1H] NMR spectra of compounds 1 (a), 6 (b), 11 (c) and 12 (d) at 293 K.
efficiency roll-off (less than 1%) at a practical luminance over
1000 cd m-2. The much lower efficiency roll-off is also ascribed
to the lower doping concentration in emitting layers for PtAu3
cluster complexes (3 wt%) than that for dpmp-supported PtAu2
complexes (8 wt%).20,21
Then, the structure of PtAg3 complex
3 was determined by
single crystal X-ray diffraction. As depicted in Figure 2a, the
structure of PtAg3 complex shows that two Ag atoms are
bridged by a chloride ion, which matches well with the 31P[1H]
NMR spectral data. Obviously, the abstraction of chloride from
CH2Cl2 provides a source of bridging chlorine atom. Such a
Results and Discussion
2 | J. Name., 2012, 00, 1-3
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phenomena has already been observed in some silver(I),28
copper(I)29 and nickel(II)30 complexes. The cationic PtAg3
cluster structure is supported by dual bridging tdpmp. Of the
four P donors in tetraphosphine, three terminal ones are
bound to Ag(I) centers whereas the central one is bonded to
platinum(II) center. All the metal atoms in PtAg3 cluster lie in
the same plane, in which three Ag atoms occupy the corners of
an approximate isosceles triangle and the Pt atom is located in
the center. The Pt−Ag distances (2.8862(7) to 3.0635(9) Å) are
much shorter than the sum of van der Waals radii of platinum
and silver atoms (3.4 Å), implying a significant intermetallic
interaction.22,23 The Ag
than 4.0 Å, which precludes the possibility of intermetallic
contact. Noticeably, the distance of Pt1 Ag1 (2.8862(7) Å) is
obviously shorter than those of Pt1 Ag2 (3.0618(8)Å) and
Pt1 Ag3 (3.0635(9) Å) as a result of Ag2 and Ag3 linked by a
chloride ion (dAg2 = 2.6373(16) Å and dAg3 = 2.6086(16) Å).
−Ag separations, however, are longer
−
−
−
−
Cl
−Cl
Fig 2 Perspective views of cationic PtAg3 complex 3 (a) and PtAu3 complex 6 (b) with
30% thermal ellipsoids. Phenyl rings of the phosphorus atoms are omitted for clarity.
The distinct asymmetry in PtAg3 cluster core is due to the
constraint from Ag2-( -Cl)-Ag3 bridging array, which results in
the much smaller angle of Ag2-Pt1-Ag3 (83.491(16) ) than
those of Ag1-Pt1-Ag2 (149.156(18) and Ag1-Pt1-Ag3
(127.340(19) ). The Pt center is located at distorted square-
planar environment composed of C2P2 chromophore. Ag1 is
coordinated to two P donors with P-Ag-P angle of 164.78(6)
whereas -Cl bridged Ag2 and Ag3 display severely distorted
tetrahedral geometry composed of CClP2 donors with the bite
angles of 82.41(11) 155.14(5)
PtAu3 complexes 10 (Scheme 1) were prepared by the
reactions of Pt(PPh3)2(C CR)2 with two equiv. tdpmp and three
ꢀ
°
°
)
°
°,
ꢀ
−
°.
6−
≡
equiv. Au(tht)Cl in the presence of three equiv. NH4ClO4.
Interestingly, the structures of PtAu3 complexes (Figure 2b)
showed dramatic variation in comparison with PtAg3
complexes (Figure 2a). In strikingly contrast to PtAg3 structures
with Pt center bound to the central P donor of tdpmp, the Pt
center in PtAu3 complexes is bonded to one of the three
terminal P donors while the central and other two terminal P
donors of tdpmp are bound to three Au centers, respectively.
The 31P[1H] NMR spectra of PtAu3 complexes (Figure 1b for
complex 6) exhibited three groups of signals centered at ca.
Fig 3 Perspective views of cationic PtAg2 complex 11 (a) and PtAu2 complex 12 (b) with
4.2−6.2, 17.8−22.7 and 29.1−30.4 ppm. The first set of signals
(Figure 1b, a) with satellite peaks (JPt-P = 2696−2706 Hz) are
ascribed to one terminal P donor of tdpmp bound to the Pt(II)
center, whereas the second one (Figure 1b, b) to the central P
donor and the later triplet (Figure 1b, c) to the other two
terminal P donors bonded to Au(I) centers.
30% thermal ellipsoids. Phenyl rings of the phosphorus atoms are omitted for clarity.
The Pt center displays
a square-planar coordination
environment composed of trans-oriented P2C2 donors. Au1
center is bound to two linearly arranged P donors with P4-Au1-
P8 angle of 179.52(14)
type coordination geometry composed of P2Cl donors with P2-
Au2-P5 and P1-Au3-P6 angles of 172.87(13) and 168.79(13)
°, while Au2 and Au3 centers, exhibit T-
As revealed by X-ray crystallography, the structure of PtAu3
complex
6
(Figure 2b) indicates that acetylides are only
Au linkages
°,
bonded to Pt center and there are no acetylide
−
respectively. The Pt1−Au1 distance (2.9619(10) Å) is much
shorter than the sum of van der Waals radii of platinum and
gold atoms (3.38 Å), suggesting a significant intermetallic
observed in PtAg3 complexes (Figure 2a). The PtAu3 cluster
atoms is on the same triangle plane, in which Au1 is located at
the center, and Pt1, Au2 and Au3 at the three apexes with Pt1-
Au1-Au2, Pt1-Au1-Au3 and Au2-Au1-Au3 angles of 127.15(4),
contact.20,21 The short Au1
(2.9769(16) Å) distances also indicate noticeable Au
−
Au2 (2.9653(10) Å) and Au1
−
−
Au3
Au
122.34(3) and 110.51(3)°, respectively. Notably, the two Au
contact. The PtAu3 structure is highly stabilized by six five-
membered coordination rings as well as significant Pt−Au and
(Au2 and Au3) atoms at triangle apexes are linked by a
bridging chloride, which was also observed even if
[Au(tht)2]ClO4 instead of Au(tht)Cl was used as the starting
precursor.
Au−Au interactions.
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The different location of Pt(C
Journal Name
≡
CR)2 moieties in PtAg3 and above, we propose that the participation of Cl− in
PtAu3 cluster complexes can be reasonably elucidated on the complexation is perturbed by a halide abstracting agent that
basis of two factors, including π−acceptor ability of acetylides destabilizes the PtM3 structure, thus resulting in the formation
towards different d10 metal ions and steric hindrance from of PtM2 species as a stable complex together with a by-product
tdpmp. It is well-known that silver(I) exhibits more [M(PPh3)x][BArF ](M = Au, x = 2; M = Ag, x = 4). Therefore, we
4
alkynophilicity than gold(I), favoring impressive
alkynes.[31] The Ag
π
acetylide linkages through
-bonding with conclude that the participation of chloride in the PtM3
-bonding structure plays a key role in stabilizing the target complexes.
−
π
facilitate and stabilize PtAg3 cluster structure (Figure 2a) with
the Pt bound to the central P donor in tdpmp so that the Pt is
located at the center of the trigonal plane of PtAg3 cluster. In
contrast, the weaker tendency to form Au
−
through -bonding renders that trans-Pt(C
acetylide linkages
CR)2 moiety in
π
≡
PtAu3 cluster is bound to one of the terminal P donor (Figure
2b) in tdpmp so that the Pt is situated at one apex in the
triangle plane of PtAu3 cluster.
Curiosities to understand the role of chloride in the
formation of PtM3 cluster structures instigated us to perform
further studies. The corresponding reactions were thus
performed in the presence of Na[BArF ] (Ar = C6H3(CF3)2),
4
which is a typical halide abstracting agent.32 As indicated in
Scheme 1, the isolated products became PtM2 heterotrinuclear
species instead of PtM3 heterotetranuclear complexes when
F
4
−
[BAr ]− was used as counterion in place of ClO4 .
The structures of PtAg2 complex 11 (Figure 3a) and PtAu2
complex 12 (Figure 3b) were determined by X-ray
crystallography. In the PtAg2 structure (Figure 3a), the trans-
Fig 4 UV-Vis absorption (in fluid CH2Cl2) and emission spectra (in doped film) of PtM3
complexes 1－10.
Pt(C≡
CC6H4But-4)2 moiety is bound to the central P donors of
Photophysical Properties
two tdpmp ligands to give a square-planar geometry. Each
Ag(I) atom is bonded to three terminal P donors of tdpmp and
one PPh3 to show a distorted tetrahedral environment.
Undoubtedly, even if the trans-Pt(C≡
CC6H4But-4)2 moiety in
the PtAg2 complex 11 is bonded to the central P donor of
tdpmp as that found in PtAg3 cluster complexes, the lack of
constraint from Ag-Cl-Ag linkage through a bridging chloride
could not sufficiently sustain the PtAg3 cluster structure.
Instead, more stable PtAg2 structure (Figure 3a) forms in the
absence of chloride ion. For PtAu2 complex 12 (Figure 3b),
PtM3 complexes 1−10 (Table 1) in CH2Cl2 exhibit intense UV
absorption bands below 290 nm, mainly due to the
tdpmp−centered π
290−360 nm is ascribed to the π
carbazole−acetylides. More importantly, a broad low-energy
bands above 400 nm (ε 1.6−1.9
104 dm3 mol−1 cm−1) is
→
π* transitions. A band centered at
→π* transitions involving
≈
×
observed, resulting most likely from aromatic acetylide-to-
platinum(II) LMCT (ligand-to-metal charge-transfer) and
aromatic acetylide-to-tdpmp LLCT (ligand-to-ligand charge
transfer) transitions.20,21,23 The low-energy absorption bands of
PtM3 complexes (Figure 4) were modulated by changing
aromatic acetylides. For PtAu3 complexes (Figure 4b), the low-
trans-Pt(C≡CC6H3(CF3)2-2,4)2 moiety is bound to the central P
atom of tdpmp, in strikingly contrast to that bonded to the
terminal P donor found in PtAu3 cluster structure. It is
noteworthy that one of the three terminal P atoms in tdpmp is
free of coordination.
energy absorption band occurs at 427 nm for
443 nm for , 470 nm for , and 472 nm for 10. Likewise, the
absorption bands due to LMCT and LLCT states in PtAg3
complexes (Figure 4a) appear at 408 nm for , 406 nm for
426 nm for , 440 nm for , and 458 nm for with almost the
same trend as PtAu3 complexes. The variation trend of low-
energy band can be interpreted on the basis of -conjugation
and -electron donating capability of aromatic acetylides.
PtM3 complexes 10 (Table 1) exhibit unstructured
emission bands at around 513 653 nm for PtAg3 complexes
(Figure S1, a) and 524 648 nm for PtAu3 complexes (Figure S1,
b) in fluid CH2Cl2 solutions. The large Stokes shifts with
microsecond range of emissive lifetimes indicate
6, 438 nm for 7,
8
9
Besides the PtM2 product, another product was also
separated through column chromatography, which was
1
2,
identified as [Au(PPh3)2][BArF ] when
M
=
Au or
4
3
4
5
[Ag(PPh3)4][BArF ] when M = Ag. However, the use of other
4
weaker boron-based anions such as [BPhF3]− or [BPh4]− as
counterion failed to give PtM2 heterotrinuclear products.
Instead, only chloride-linked PtM3 heterotetranuclear cluster
complexes were isolated. It should be emphasized that in the
π
π
1−
−
presence of Na[BArF ], only PtM2 complexes could be isolated,
4
−
independent of the reactant ratios while PtM3 cluster
complexes could never be obtained. When we attempted to
use an excess of Au(tht)Cl or Ag(tht)ClO4, we obtained PtM2
complexes together with [M4(tdpmp)2]4+ as the major products
reported elsewhere.33 From the investigation mentioned
a
phosphorescent nature with triplet excited states. The
emission origin is assigned as the aromatic acetylide-to-
4 | J. Name., 2012, 00, 1-3
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Table 1. The UV-Vis absorption and photoluminescent data for PtM3 cluster complexes 1−10.
complex
λabsa/nm (ε/dm3 mol−1 cm−1
)
medium
λ
em/nm (τ/ꢀs)
ΦPL/%
1
292 (94670), 321 (84310), 340 (66780), 408 (26870)
CH2Cl2
541 (3.11)
590 (3.46)
522 (4.58)
<0.3
<0.3
0.8
Powder
mCP:OXD-7b
2
3
4
5
6
7
8
9
268 (105300), 318 (46210), 406 (16290)
CH2Cl2
513 (2.61)
530 (2.99)
472 (2.34)
<0.3
<0.3
<0.3
Powder
mCP:OXD-7b
262(121360), 334 (81610), 426 (20580)
CH2Cl2
585 (2.11)
604 (2.69)
560 (4.41)
<0.3
<0.3
0.6
Powder
mCP:OXD-7b
292 (90800), 304 (77390), 339 (44780), 440 (14040)
268 (89380), 320 (45030), 458 (15870)
CH2Cl2
562 (2.39)
590 (2.56)
533 (5.43)
<0.3
<0.3
2.1
Powder
mCP:OXD-7b
CH2Cl2
653 (1.92)
687 (2.32)
616 (5.39)
<0.3
<0.3
3.0
Powder
mCP:OXD-7b
292 (88560), 344 (48980),368 (48180), 427 (16010)
263 (111800), 368 (48560), 438 (15590)
CH2Cl2
524(2.53)
570 (3.41)
512(4.90)
1.1
Powder
mCP:OXD-7b
5.1
90.5
CH2Cl2
528(2.13)
544(2.39)
522 (3.37)
2.6
Powder
mCP:OXD-7b
2.8
68.3
256(114135), 330 (58018), 373 (41583), 443 (19136)
CH2Cl2
550 (2.88)
575 (3.60)
543 (5.11)
2.6
Powder
mCP:OXD-7b)
7.8
88.4
281 (104600), 292 (118300), 340 (44660), 366 (43370), 470 CH2Cl2
565(2.37)
592 (3.49)
559(4.64)
9.7
(19780)
Powder
mCP:OXD-7b
9.3
89.3
10
267 (89690), 365 (35630), 472 (16430)
CH2Cl2
648(1.86)
650 (2.18)
590 (5.90)
2.9
Powder
mCP:OXD-7b
2.4
76.8
a
Absorption spectra were measured in degassed CH2Cl2 solutions with a concentration of 1 × 10−5 M. Absolute quantum yields in powder, films and CH2Cl2 solutions
were determined by the integrating sphere (142 mm in diameter). b Doped in 48.5 wt% mCP : 48.5 wt% OXD-7 with 3 wt% PtM3 complex.
platinum(II) 3LMCT and aromatic acetylide-to-tdpmp 3LLCT complexes display much stronger photoluminescence than the
transitions. It is noteworthy that the emission energy of 3LMCT corresponding PtAg3 complexes (Table 1) in both solution and
and 3LLCT is closely related to the
aromatic acetylides. With stronger electron donating Ag
phenothiazine attached to acetylide, the emission bands of serves as a main non-radiative deactivation pathway of the
PtM3 complexes (653 nm) and 10 (648 nm) show obvious triplet excited state.
red-shifts compared to those of carbazole-containing The emission spectra of spin-coated films composed of 3
complexes (550 585 nm). It is noticeable that PtAu3 wt% PtAu3 complex doped in mixed host mCP : OXD-7 (1 : 1)
π
-electron donating ability of solid state. This is likely due to the lability of Ag
−Cl and
−
Cacetylide bonds in PtAg3 cluster complexes, which may
5
−
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3
3
are centered at 512−590 nm with photoluminescent quantum (tdpmp) LLCT and
π
(aromatic acetylide)
→
s/p (PtM3) LMCT
yields (PLQYs) of 68.3−90.5% (Table 1). Almost identical states, mixed with minor intraligand (3IL) character of aromatic
emission spectra of the doped films to those of the acedylide. It is noteworthy that PtAg3 complexes and
corresponding PtAu3 complexes in CH2Cl2 solutions with a display more intraligand (IL) character of aromatic acetylides
microsecond region of emissive lifetimes demonstrate a highly than PtAu3 complexes and in both lowest-energy singlet
1
3
6
8
efficient energy transfer from organic host materials to PtAu3 and triplet excited states.
complexes. However, by comparison of the wavelength range
and contour of the emission spectra in PtAg3 complexes
(Figure 4c) with those in corresponding PtAu3 complexes
(Figure 4d), the emission energies are comparable but the
quantum yields in the formers are quite low (
< 3.0%) even
after doping with different host materials. The high PLQYs of
PtAu3 complexes ranging from 68.3% to 90.5% in mCP : OXD-7
doped films suggest that they are promising dopants for
phosphorescent OLED applications.
The absolute HOMO energy of PtAu3 complexes 8−10 was
determined by electrochemical studies (Figure S2). Anodic
sweep shows an irreversible oxidation wave at around +0.80 V
with insignificant shifts of the potentials upon modification of
aromatic acetylides, assigned as the metal-centered oxidation.
Another quasi-reversible oxidation wave at around +1.10 V can
be ascribed to the carbazole-based oxidation.34 The HOMO
Fig 5 The transition orbital distribution (iso value = 0.0004) in the lowest-energy triplet
excited state for PtM3 complexes 1, 3, 6 and 8 in CH2Cl2. The blue-green and purple
regions represent electron depletion (ED) and electron accumulation (EA) in the
energy levels of PtAu3 complexes
5.25, 5.26 and 5.23 eV, respectively. The optical band gap
of 2.55 eV ( ), 2.51 eV ( ) and 2.47 eV (10) were extracted
8−10 were calculated to be
−
−
−
transition orbitals, respectively
.
8
9
Table 2. Performance data of solution-processed OLEDs based on PtAu3 complexes.a
from the UV-Vis absorption edge of the corresponding
complexes. Adding this band gap to the HOMO energy affords
compound
8
9
10
a LUMO level of
−2.70, −2.75 and −2.76 eV (Table S9) for PtAu3
λ
EL /nm
Vonb /V
541
556
588
complexes 10, respectively.
8−
5.2
5.5
4.9
c
2
Lmax /cd m−
CEmax /cd A−
PEmax /lm W−
EQEmaxf /%
CIE
10911
58.3
26.1
14.9
0.33, 0.61
12711
62.8
25.1
17.7
0.24, 0.51
19308
45.2
Theoretical Computational Studies
d
1
e
1
20.3
In order to get more insight to the transition characteristics in
absorption and emission properties, density functional theory
(DFT) and time-dependent DFT (TD-DFT) calculations were
carried out using PBE1PBE functional (for computational
18.1
0.47, 0.52
a
Device structure is ITO / PEDOT : PSS (50 nm) / mCP (48.5 wt%) : OXD-7 (48.5
details, see ESI). The orbital plots depicted in Figure S5 show wt%) : PtAu3 complex (3 wt%) (50 nm) / BmPyPb (50 nm) / LiF(1 nm) / Al (100
b
c
d
nm). Turn-on voltage at 1 cd m−2. Maximum luminance. Maximum current
that the HOMO focuses predominately on aromatic acetylides
(>80% population) with some distribution at PtM3 centers
(<12% population) while the LUMO is mostly spread over
tdpmp and PtM3 cluster centers with minor population at
aromatic acetylides. The calculations predict that the lowest-
efficiency. e Maximum power efficiency. f Maximum external quantum efficiency.
Solution-Processed OLEDs
Solution-processable OLEDs based on PtAu3 complexes 8−10
as phosphorescent dopants were investigated using three
layer device configuration: ITO / PEDOT : PSS (50 nm) / host :
PtAu3 complex (50 nm) / ETL (50 nm) / LiF (1 nm) / Al (100 nm).
energy absorption at 431 nm for
and 400 nm for (Tables S1, S3, S5 and S7, SI) correlate well
with the experimentally measured data. In all the cases, the S0
S1 transition primarily originates from the HOMO LUMO
(HOMO LUMO+1 for complex ), which mainly corresponds
1, 445 nm for 3, 405 nm for 6
8
The
poly(3,4-ethylenedioxythiophene)
:
poly(styrene-
→
→
sulfonate) (PEDOT: PSS) was used as a hole-injection layer
through spin coating in an aqueous solution. Based on the
→
8
to an admixture of LLCT/LMCT character. The calculated
HOMO (
levels of PtAu3 complexes
TCTA (HOMO: 5.83 eV) and OXD-7 (LUMO:
−
5.23 to
−
5.26 eV) and LUMO (
10, mCP (HOMO: -5.90 eV) or
2.80 eV) were
−2.70 to -2.76 eV)
excited energies from the ground state to the first triplet
8−
excited state are 2.18 eV for
2.38 eV for , which correspond to the emission wavelengths
of 569 nm for , 591 nm for , 509 nm for and 522 nm for
These values coincide well with the experimental data in
CH2Cl2 solutions (541 nm for , 585 nm for , 524 nm for and
550 nm for ). As indicated in Figure 5, the transition of HOMO
LUMO in lowest-energy triplet states (Tables S2, S4, S6 and
1, 2.10 eV for 3, 2.44 eV for 6 and
−
−
8
selected to act as blended host materials. To improve the
charge balance in the recombination zone, an additional layer
with BmPyPb, TPBi or BCP was prepared through thermal
deposit to serve as electron transport or hole-blocking layer,
then capped with LiF/Al cathode. The HOMO and LUMO levels
of the materials used in the devices are schematically depicted
in Figure S4. The corresponding electroluminescent (EL) data
1
3
6
8.
1
3
6
8
→
S8, SI) is mainly featured with
π (aromatic acetylide) → π*
6 | J. Name., 2012, 00, 1-3
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are listed in Table 2. The emissive layer was prepared by spin- roll-off of 0.6%, 1.1% and 8.8%, respectively. The outstanding
coating dichloromethane solution of mCP (48.5 wt%) : OXD-7 device performance is owing to better charge carrier balance
(48.5 wt%) : PtAu3 complex (3 wt%).
in the bipolar host interface and negligible exciton annihilation
of the dopants with a low doping concentration (3 wt%). It is
worth mentioning that the ultra-low EQE roll-off realized in
these devices with high EQE (over 18 %) from PtAu3 complexes
is the one among the best solution-processed phosphorescent
OLEDs (PHOLEDs).36
Conclusions
A family of tetraphosphine-supported PtM3 (M = Au, Ag)
cluster complexes stabilized by chloride ion abstracted from
dichloromethane were prepared and characterized
structurally. The bonding difference between gold(I) and
silver(I) to acetylide lead to the formation of totally different
PtM3 cluster structures. In contrast to that bound to one of the
terminal P donors of P(CH2PPh2)3 in PtAu3 cluster due to steric
effect, the Pt(C
through the central P donor in PtAg3 cluster complexes,
stabilized by the additional Ag acetylide bonding
≡CR)2 moiety is associated with P(CH2PPh2)3
Fig 6 (a) J−V−L characteristics of the devices based on PtAu3 complexes 8−10. (b)
Current efficiency vs luminance (c) EQE vs luminance.(d) Photoluminescent (PL) spectra
(dash) in light-emitting layers and electroluminescent (EL) spectra (solid) of the devices.
−
π
interaction. Introducing sodium tetrakis[3,5-bis(trifluoro-
methyl)phenyl]borate as a halide abstracting agent resulted
only in the isolation of PtM2 complexes. The phosphorescent
emission in PtAu3 complexes is much stronger than that of
PtAg3 complexes because of fluxional structures for the latter.
Superior electroluminescence with EQE up to 18.1% is
successfully achieved using PtAu3 cluster complexes as
phosphorescent dopants to fabricate solution-processable
OLEDs. Most importantly, the optimized devices demonstrate
high-efficiency EL performance with extremely small EQE roll-
off at practical brightness over 1000 cd m-2.
The EL spectra show the emission maxima at 541 nm for
556 nm for , and 588 nm for 10, coinciding perfectly with the
corresponding PL spectra of the emitting films centered at 543
nm for , 559 nm for , and 590 nm for 10. The excitons are
8,
9
8
9
completely confined within the emissive layer and charge
carrier recombination takes place only in emissive layers of the
devices. The low doping concentration (3 wt%) of PtAu3
complexes prevents π–π interactions between the dopant
molecules in devices.35 As depicted in Figure 6 and Table 2, the
optimized devices based on PtAu3 complex
8 show superior
performance with maximum CE of 58.3 cd A-1 and power
efficiency (PE) of 26.1 lm W-1, corresponding to peak EQE of
14.9%. The Commission Internationale de L’Eclairage (CIE)
chromaticity coordinates (x, y) were evaluated to be (0.33,
0.61), in close proximity to pure green color. Likewise, the
optimized devices give a peak CE of 62.8 cd A−1, PE of 25.1 lm
Experimental Section
General Procedures and Materials
All reactions were operated under dry argon using Schlenk techniques and
vacuumꢀline systems. Solvents were carefully dried and distilled from
appropriate drying agents prior to use. Commercially available reagents were
used without further purification unless stated otherwise. Sonogashira
coupling reactions were utilized to prepare the alkynyl ligands such as 9ꢀ(4ꢀ
ethynylphenyl)ꢀ9Hꢀcarbazole (HC≡Cꢀ4ꢀC6H4Carb−9), 9ꢀphenylꢀ2ꢀethynylꢀ
9H ꢀcarbazole (HC≡Cꢀ2ꢀPhCarb−9), 9ꢀ(4ꢀ(9Hꢀcarbazolꢀ9ꢀyl)phenyl)ꢀ3ꢀ
ethynylꢀ9Hꢀcarbazole (HC≡Cꢀ3ꢀCarbPhCarbꢀ9), 10ꢀethylꢀ3ꢀethynylꢀ10Hꢀ
phenothiazine (HC≡Cꢀ3ꢀEtPTZꢀ9). The precursor complexes Pt(PPh3)2(C≡Cꢀ
4ꢀC6H4ꢀCarb−9)2, Pt(PPh3)2(C≡CC6H4Butꢀ4)2, Pt(PPh3)2(C≡Cꢀ2ꢀPhCarb−9)2,
Pt(PPh3)2(C≡Cꢀ3ꢀCarbPhCarbꢀ9)2, and Pt(PPh3)2ꢀ(C≡Cꢀ3ꢀEtPTZꢀ9)2 were
prepared by reactions of Pt(PPh3)2Cl2 (0.5 mmol), corresponding alkynyl
ligands (1.1 mmol), CuI (1 mg) and NEt3 (1 mL) in chloroform (50 mL) with
W−1 and EQE of 17.7 % for complex
A−1, PE of 20.3 lm W−1 and EQE of 18.1 % for complex 10. The
performance improvement in CE and EQE for PtAu3 complex
(62.8 cd A−1 and 17.7%) relative to those for (58.3 cd A-1 and
9, and peak CE of 45.2 cd
9
8
14.9%) is presumably derived from the incorporation of one
more hole-transport carbazole group, where a better balance
in the electron and hole carriers at the emissive interface leads
to better device efficiency.
Remarkably, all the devices showed an extremely low
efficiency roll-off at practical brightness. The EQE of devices
stirring at 50 oC for
5 h. The procedure for the synthesis of
doped with PtAu3 complex
luminance of 1000 cd m-2, corresponding to EQE roll-off of
3.4%. Likewise, the devices based on PtAu3 complex also
8 remains as high as 14.4% at
tris((diphenylphosphino)methyl)phosphine (tdpmp) followed the methods
reported in the literatures.38,39 All reactions were monitored by using thinꢀ
layer chromatography (TLC) with Merck precoated glass plates. The
products were visualized with UVꢀlight irradiation at 254 and 365 nm.
9
keeps the EQE of 17.1% with a quite low efficiency roll-off of
3.4% at the practical luminance of 1000 cd m-2. More
importantly, the devices based on PtAu3 complex 10 displays
ultra-low efficiency roll-off. At a luminance of 1000, 2000 and
5000 cd m-2, the EQE is 18%, 17.9% and 16.5% with efficiency
[PtAg3(ꢀ-Cl)(tdpmp)2(C≡C-4-C6H4Carb−9)2](ClO4)2 (1). A mixture of
Pt(PPh3)2(C≡Cꢀ4ꢀC6H4Carb−9)2 (62.6 mg, 0.05 mmol), tdpmp (62.8 mg, 0.1
mmol), and Ag(tht)ClO4 (45 mg, 0.15 mmol) was added to CH2Cl2 (30 mL)
and the solution was stirred at ambient temperature for 8 h. The product was
then purified by chromatography on a silica gel column using CH2Cl2ꢀMeOH
This journal is © The Royal Society of Chemistry 20xx
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ARTICLE
Journal Name
(v/v = 20 : 1) as the eluent to give pure sample. Yield: 76%. 1H NMR (CDCl3, (d, 4H, J = 8.4 Hz), 4.17 (br, 4H), 3.67 (br, 8H). 31P[1H] NMR (CDCl3, ppm):
ppm): 8.20 (d, 4H, J = 7.8 Hz), 7.87−7.91 (m, 8H), 7.69−7.72 (m, 14H), 30.4 (t, 4P, JP−P = 31 Hz), 22.7 (m, 2P, JP−P = 25 Hz), 4.2 (t, 2P, JP−P = 25 Hz,
7.48−7.51 (m, 10H), 7.35−7.38 (m, 10H), 7.29−7.33 (m, 18H), 7.20−7.23 (m, JPt−P = 2676 Hz). HRMS (ESI): m/z calculated for C118H96Au3ClN2P8Pt
12H), 6.66 (t, 4H, J = 6.4 Hz), 5.19 (d, 4H, J = 8.4 Hz), 4.17 (br, 4H), 3.46 [M−2ClO4]2+: 1305.1880; found: 1305.1839. IR (KBr, cm−1): 2107w (C≡C),
(br, 8H). 31P[1H] NMR (CDCl3, ppm): 19.3 (m, 2P, JP−P = 27 Hz, JPt−P = 2402 1100s (ClO4−).
Hz), 9.6 (m, 2P, JP−P = 37 Hz), −0.6 (m, 4P). HRMS (ESI): m/z calculated for
118H96Ag3ClN2P8Pt [M−2ClO4]2+: 1172.0958; found: 1172.0993. IR (KBr,
[PtAu3(ꢀ-Cl)(tdpmp)2(C≡CC6H4But-4)2](ClO4)2 (7). This compound was
prepared by the same synthetic procedure as that of 6 except for the use of
Pt(PPh3)2(C≡CC6H4Butꢀ4)2 instead of Pt(PPh3)2(C≡Cꢀ4ꢀC6H4Carb−9)2. Yield:
C
−
cm−1): 2084w (C≡C), 1098s (ClO4 ).
[PtAg3(ꢀ-Cl)(tdpmp)2(C≡CC6H4But-4)2](ClO4)2 (2). This compound was 72%. 1H NMR (CDCl3, ppm): 7.89−7.93 (m, 8H), 7.74−7.77 (m, 8H),
prepared by the same synthetic procedure as that of 1 except for the use of 7.66−7.70 (m, 8H), 7.49−7.52 (m, 14H), 7.31−7.34 (m, 14H), 7.02−7.05 (m,
Pt(PPh3)2(C≡CC6H4Butꢀ4)2 instead of Pt(PPh3)2(C≡Cꢀ4ꢀC6H4Carb−9)2. Yield: 8H), 6.54 (d, 4H, J = 8 Hz), 5.41 (d, 4H, J = 8 Hz), 4.08 (br, 4H), 3.85 (br,
84%. 1H NMR (CDCl3, ppm): 7.74−7.78 (m, 14H), 7.53−7.56 (m, 10H), 4H), 3.54 (br, 4H) 0.98−1.2 (m, 18H). 31P[1H] NMR (CDCl3, ppm): 29.1 (t,
7.43−7.46 (m, 4H), 7.29−7.33 (m, 14H), 7.18−7.21 (m, 10H), 7.09−7.12 (m, 4P, JP−P = 32 Hz), 17.8 (m, 2P, JP−P = 30 Hz), 4.8 (t, 2P, JP−P = 27 Hz, JPt−P
=
8H), 6.20 (d, 4H, J = 8 Hz), 4.91 (d, 4H, J = 8 Hz), 3.96 (br, 4H), 3.31 (br, 2694 Hz). HRMS (ESI): m/z calculated for C102H98Au3ClN2P8Pt
4H), 3.10 (br, 4H), 0.96−1.2 (m, 18H). 31P[1H] NMR (CDCl3, ppm): 19.1 (m, [M−2ClO4]2+: 1196.1927; found: 1196.1925. IR (KBr, cm−1): 2105w (C≡C),
2P, JP−P = 27 Hz, JPt−P = 2344 Hz), 9.0 (m, 2P, JP−P = 38 Hz), −4.0 (m, 4P). 1100s (ClO4−).
HRMS (ESI): m/z calculated for C102H98Ag3ClP8Pt [M−2ClO4]2+: 1063.1005;
−
found: 1063.1009. IR (KBr, cm−1): 2082w (C≡C), 1098s (ClO4 ).
[PtAu3(ꢀ-Cl)(tdpmp)2(C≡C-2-PhCarb−9)2](ClO4)2 (8). This compound
was prepared by the same synthetic procedure as that of 6 except for the use
[PtAg3(ꢀ-Cl)(tdpmp)2(C≡C-3-EtCarb−9)2](ClO4)2 (3). This compound of transꢀPt(PPh3)2(C≡Cꢀ2ꢀPhCarb−9)2 instead of Pt(PPh3)2(C≡Cꢀ4ꢀ
was prepared by the same synthetic procedure as that of 1 except for the use C6H4Carb−9)2. Yield: 66%. 1H NMR (CDCl3, ppm): 8.01−8.03 (m, 8H),
of transꢀPt(PPh3)2(C≡Cꢀ3ꢀEtCarb−9)2 instead of Pt(PPh3)2(C≡Cꢀ4ꢀ 7.74−7.77 (m, 10H), 7.66−7.69 (m, 10H), 7.51−7.55 (m, 12H), 7.43−7.49 (m,
C6H4Carb−9)2. Yield: 75%. 1H NMR (CDCl3, ppm): 7.81−7.84 (m, 8H), 12H), 7.37−7.41 (m, 16H), 6.95 (m, 10H), 6.78 (d, 2H, J = 8.4 Hz), 6.02 (s,
7.72−7.75 (m, 6H), 7.64−7.67 (m, 8H), 7.37−7.40 (m, 6H), 7.32−7.36 (m, 2H), 5.78 (d, 2H, J = 8.4 Hz), 4.13 (br, 4H), 4.03 (br, 4H), 3.65 (br, 4H).
12H), 7.24−7.27 (m, 6H), 7.19−7.22 (m, 12H), 7.07−7.10 (m, 10H), 6.32 (d, 31P[1H] NMR (CDCl3, ppm): 29.6 (t, 4P, JP−P = 32 Hz), 18.1 (m, 2P, JP−P = 30
2H, J = 8.6 Hz), 5.96 (s, 2H), 5.11 (d, 2H, J = 8.2 Hz), 4.29 (q, 4H, J = 7.2 Hz), 6.2 (t, 2P, JP−P = 30 Hz, JPt−P = 2726 Hz). HRMS (ESI): m/z calculated
Hz), 4.25 (br, 4H), 3.45 (br, 4H), 3.29 (br, 4H), 1.43 (t, 6H, J = 7.2 Hz). for C118H96Au3ClN2P8Pt [M−2ClO4]2+: 1305.1880; found: 1305.1909. IR
−
31P[1H] NMR (CDCl3, ppm): 18.9 (m, 2P, JP−P = 28 Hz, JPt−P = 2406 Hz), 9.3 (KBr, cm−1): 2099w (C≡C), 1100s (ClO4 ).
(m, 2P, JP−P = 37 Hz), −1.8 (m, 4P, JP−P = 31 Hz). HRMS (ESI): m/z
calculated for C110H96Ag3ClN2P8Pt [M−2ClO4]2+: 1124.0958; found:
[PtAu3(ꢀ-Cl)(tdpmp)2(C≡C-3-CarbPhCarb-9)2] (ClO4)2 (9). This
−
1124.0975. IR (KBr, cm−1): 2071w (C≡C), 1098s (ClO4 ).
compound was prepared by the same synthetic procedure as that of 6 except
for the use of transꢀPt(PPh3)2(C≡Cꢀ3ꢀCarbPhCarbꢀ9)2 instead of
[PtAg3(ꢀ-Cl)(tdpmp)2(C≡C-3-CarbPhCarb-9)2] (ClO4)2 (4). This Pt(PPh3)2(C≡Cꢀ4ꢀC6H4Carb−9)2. Yield: 65%. 1H NMR (CDCl3, ppm): 8.23 (d,
compound was prepared by the same synthetic procedure as that of 1 except 4H, J = 7.6 Hz), 8.04−8.07 (m, 8H), 7.87−7.90 (m, 6H), 7.76−7.81 (m, 18H),
for the use of Pt(PPh3)2(C≡Cꢀ3ꢀCarbPhCarbꢀ9)2 instead of Pt(PPh3)2(C≡Cꢀ4ꢀ 7.58−7.61 (m, 10H), 7.48−7.52 (m, 14H), 7.42−7.47 (m, 20H), 7.02−7.05 (m,
C6H4Carbꢀ9)2. Yield: 72%. 1H NMR (CDCl3, ppm): 8.24 (d, 2H, J = 7.8 Hz), 10H), 6.95 (d, 4H, J = 8.6 Hz), 6.05 (s, 2H), 5.91 (d, 2H, J = 8.6 Hz), 4.16 (br,
7.91−7.94 (m, 12H), 7.73−7.78 (m, 18H), 7.62−7.65 (m, 4H), 7.51−7.54 (m, 4H), 4.06 (br, 4H), 3.68 (br, 4H). 31P[1H] NMR (CDCl3, ppm): 29.7 (t, 4P,
8H), 7.40−7.44 (m, 8H), 7.31−7.35 (m, 16H), 7.24−7.27 (m, 14H), 7.13−7.16 JP−P = 32 Hz), 18.2 (m, 2P, JP−P = 30 Hz), 6.2 (t, 2P, JP−P = 27 Hz, JPt−P = 2706
(m, 10H), 6.47 (d, 2H, J = 8.6 Hz), 6.05 (s, 2H), 5.15 (d, 2H, J = 7.8 Hz), Hz). HRMS (ESI): m/z calculated for C142H110Au3ClN4P8Pt [M− 2ClO4]2+:
4.28 (br, 4H), 3.48 (br, 4H), 3.33 (br, 4H). 31P[1H] NMR (CDCl3, ppm): 18.9 1470.7458; found: 1470.7484. IR (KBr, cm−1): 2104w (C≡C), 1100s (ClO4−).
(m, 2P, JP−P = 27 Hz, JPt−P = 2302 Hz), 9.3 (m, 2P, JP−P = 37.6 Hz), −3.4 (m,
4P, JP−P = 28 Hz). HRMS (ESI): m/z calculated for C142H110Ag3ClN4P8Pt
[PtAu3(ꢀ-Cl)(tdpmp)2(C≡C-3-EtPTZ-9)2](ClO4)2 (10). This compound
[M−2ClO4]2+: 1337.1536; found: 1337.1550. IR (KBr, cm−1): 2071w (C≡C),
was prepared by the same synthetic procedure as that of 6 except for the use
−
1098s (ClO4 ).
of Pt(PPh3)2(C≡Cꢀ3ꢀEtPTZꢀ9)2 instead of Pt(PPh3)2(C≡Cꢀ4ꢀC6H4Carb−9)2.
1
Yield: 70%. H NMR (CDCl3, ppm): 7.87−7.89 (m, 8H), 7.74−7.77 (m, 8H),
[PtAg3(ꢀ-Cl)(tdpmp)2(C≡C-3-EtPTZ-9)2](ClO4)2 (5). This compound 7.66−7.69 (m, 8H), 7.48−7.51 (m, 12H), 7.36−7.39 (m, 12H), 7.12−7.15 (m,
was prepared by the same synthetic procedure as that of 1 except for the use 16H), 6.95 (t, 2H, J = 7.2 Hz), 6.86 (d, 2H, J = 8.2 Hz), 6.18 (d, 2H, J = 8.4
of Pt(PPh3)2(C≡Cꢀ3ꢀEtPTZꢀ9)2 instead of Pt(PPh3)2(C≡Cꢀ4ꢀC6H4Carbꢀ9)2. Hz), 5.35 (d, 2H, J = 8.4 Hz), 5.04 (s, 2H), 4.04 (br, 4H), 3.93 (br, 4H), 3.84
Yield: 78%. 1H NMR (CDCl3, ppm): 8.05 (d, 2H, J = 7.8 Hz), 7.91−7.94 (m, (q, 4H, J = 7.0 Hz), 3.54 (br, 4H), 1.41 (t, 6H, J = 7.0 Hz). 31P[1H] NMR
8H), 7.72−7.76 (m, 6H), 7.54−7.57 (m, 8H), 7.38−7.42 (m, 10H), 7.23−7.28 (CDCl3, ppm): 29.6 (t, 4P, JP−P = 32 Hz), 18.4 (m, 2P, JP−P = 30 Hz), 5.8 (t,
(m, 20H), 7.13−7.16 (m, 6H), 7.01−7.04 (m, 10H), 5.58 (s, 2H), 5.05 (d, 2H, 2P, JP−P = 29 Hz, JPt−P = 2706 Hz). HRMS (ESI): m/z calculated for
J = 8.2 Hz), 4.23 (br, 4H), 3.39 (q, 4H, J = 7.2 Hz), 3.23 (br, 8H), 1.05 (t, 6H, C110H96Au3ClN2P8PtS2 [M−2ClO4]2+: 1289.1600; found: 1289.1617. IR (KBr,
−
J = 7.2 Hz). 31P[1H] NMR (CDCl3, ppm): 18.0 (m, 2P, JP−P = 27 Hz, JPt−P
=
cm−1): 2099w (C≡C), 1100s (ClO4 ).
2336 Hz), 9.1 (m, 2P, JP−P = 31 Hz), −2.2 (m, 4P). HRMS (ESI): m/z
calculated for C110H96Ag3ClN2P8PtS2 [M−2ClO4]2+: 1156.0678; found:
[PtAg2(tdpmp)2(PPh3)2(C≡CC6H4But-4)2](BArF
)
(11). A mixture of
2
4
−
1156.0700. IR (KBr, cm−1): 2092w (C≡C), 1096s (ClO4 ).
Pt(PPh3)2(C≡CC6H4Butꢀ4)2 (51.7 mg, 0.05 mmol), tdpmp (62.8 mg, 0.1
mmol), Ag(tht)ClO4 (45 mg, 0.15 mmol) and NaBArF4 (133 mg, 0.15 mmol)
[PtAu3(ꢀ-Cl)(tdpmp)2(C≡C-4-C6H4Carb-9)2](ClO4)2 (6). A mixture of was added to CH2Cl2 (30 mL) and the solution was stirred at ambient
Pt(PPh3)2(C≡Cꢀ4ꢀC6H4Carbꢀ9)2 (62.6 mg, 0.05 mmol), tdpmp (62.8 mg, 0.1 temperature for 8 h. The product was then purified by chromatography on a
mmol), Au(tht)Cl (48 mg, 0.15 mmol), NH4ClO4 (18 mg, 0.15 mmol) was silica gel column using Petroleum ether : CH2Cl2 (v/v = 1 : 1) as the eluent to
added to CH2Cl2 (30 mL) and the solution was stirred at ambient temperature give pure sample. yield 74%; 1H NMR (CD3CN, ppm): 7.74 (m, 18H), 7.52
for 8 h. The product was then purified by chromatography on a silica gel (m, 24H), 7.47 (d, 4H, J = 8.4 Hz), 7.31 (m, 4H), 7.28 (m, 22H), 7.18 (d, 4H,
column using CH2Cl2ꢀMeOH (v/v = 20 : 1) as the eluent to give pure solid. J = 8.4 Hz), 6.97 (m, 22H), 6.91 (m, 24H), 3.60 (br, 12H), 1.32 (s, 18H). 31
P
Yield: 68%. 1H NMR (CDCl3, ppm): 8.18 (d, 4H, J = 7.8 Hz), 7.93−7.97 (m, NMR (CD3CN, ppm): 16.9 (m, 1P), 14.5 (m, 1P), ꢀ2.8 (s, 2P, JPt−P = 2434 Hz),
16H), 7.72 (d, 8H, J = 6.8 Hz), 7.50−7.54 (m, 16H), 7.39−7.42 (m, 14H), ꢀ14.9 (m, 3P), ꢀ16.1 (m, 3P). 19F NMR (CD3CN, ppm): ꢀ62.3 (s). HRMS
7.31−7.34 (m, 10H), 7.16 (t, 8H, J = 7.6 Hz), 6.90 (d, 4H, J = 8.4 Hz), 5.70
8 | J. Name., 2012, 00, 1-3
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(ESI): m/z calculated for C138H128Ag2P10Pt [M − 2BArF ]2+: 1253.2547; properties, 80 singlet and 6 triplet excitedꢀstates were calculated, respectively,
4
found: 1253.2581.
based on the optimized structures in the ground state and lowestꢀenergy
triplet state to determine the vertical excitation energies by timeꢀdependent
density functional theory (TDꢀDFT)42 with the same functional used in the
optimization process. In the calculation of excited states, the polarizable
continuum model method (PCM)43 using CH2Cl2 as the solvent was employed.
The selfꢀconsistent field (SCF) convergence criterions of RMS density matrix
and maximum density matrix were set at 10ꢀ8 and 10ꢀ6 a.u., respectively, in
excitedꢀstate calculation. The iterations of excited states continue until the
changes on energies of states were no more than 10ꢀ7 a.u. between the
iterations, and then convergences were reached in all the excited states. In
these calculations, the StuttgartꢀDresden (SDD)44 basis set and the effective
core potentials (ECPs) were used to describe the Pt, Ag and Au atoms. Other
nonꢀmetal atoms of Cl, P, N, C and H were described by the allꢀelectron basis
set of 6ꢀ31G*. Visualization of the frontier molecular orbitals and the
transition orbital distribution were performed by GaussView. Ros & Schuit
method45 (Cꢀsquared population analysis method, SCPA) was supported to
analyze the partition orbital composition by using Multiwfn 3.3.8 program.46
[PtAu2(tdpmp)2(C≡C- Ph(2,4-CF3)2](Cl)(BArF
) (12). A mixture of
4
Pt(PPh3)2(C≡CPh(2,4ꢀCF3)2 (59.6 mg, 0.05 mmol), tdpmp (62.8 mg, 0.1
mmol), Au(tht)Cl (48 mg, 0.15 mmol), NaBArF (133 mg, 0.15 mmol) was
4
added to CH2Cl2 (30 mL) and the solution was stirred at ambient temperature
for 8 h. The product was then purified by chromatography on a silica gel
column using Petroleum ether : CH2Cl2 (v/v = 1 : 1) as the eluent to give pure
1
solid.yield 62%; H NMR (CD3CN, ppm): 7.77 (s, 2H), 7.71 (br, 16H), 7.69
(s, 8H), 7.51 (br, 20H), 7.41 (s, 2H), 7.38 (d, 10H, J = 7.6 Hz), 7.30 (t, 18H, J
= 7.6 Hz), 6.20 (d, 2H, J = 8.4 Hz), 3.66 (br, 12H). 31P NMR (CD3CN, ppm):
11.6 (br, 6P), 3.6 (m, 2P, JPt−P = 2426 Hz). 19F NMR (CD3CN, ppm): ꢀ61.8 (s),
ꢀ63.2 (s), ꢀ63.4 (s). HRMS (ESI): m/z calculated for C98H78Au2F12P8Pt [M −
(Cl)(BArF )]2+: 1160.1372; found: 1160.1405.
4
Physical Measurements. 1H and 31P NMR spectra were performed on a
Bruker Avance III (400 MHz) spectrometer with SiMe4 as the internal
reference and H3PO4 as the external reference, respectively. Chemical shifts
are reported in parts per million (ppm) downfield from residual solvent peaks
and coupling constants are reported as Hertz (Hz). Splitting patterns are
designated as singlet (s), doublet (d) and triplet (t). Splitting patterns that
could not be interpreted or easily visualized are designated as multiplet (m)
and broad (br). UVꢀVis absorption spectra were measured on a PerkinꢀElmer
Lambda 35 UVꢀVis spectrophotometer using a 10 mm path quartz cell.
Device Fabrication and characterization: ITO substrates were cleaned
by detergent and deionized water, then successively washed by ethanol,
acetone and isopropanol under ultrasonic, respectively, followed by UVꢀ
ozone treatment for 15 min. A PEDOT : PSS solution was spinꢀcoated on the
o
ITO substrates at 4800 r/min for 1 min, which were then dried at 140 C for
20 min. The emitting layers were prepared using filtered CH2Cl2 solutions (5
mg/mL) composed of host and PtAu3 compound through spinꢀcoating at 2000
r/min for 30 s. Subsequently, ETL (0.3 nm/s), LiF (0.05 nm/s) and Al (3
nm/s) were thermally evaporated in a vacuum chamber at a base pressure
lower than 4.0 × 10−4 Pa. The current densityꢀvoltageꢀbrightness (IꢀVꢀB)
characetrists of the devices were measured on a Keithley 2400/2000 source
meter with a calibrated silicon photodiode. All the measurements of the
devices were perfomed at dry and ambient conditions with humidity lower
than 30%.
Infrared spectra (IR) were recorded on
a
Magna 750 FTꢀIR
spectrophotometer. Highꢀresolution mass spectrometry (HRMS) was
recorded on an Impact II mass spectrometer using dichloromethane and
methanol mixtures as mobile phases. The excitation and emission spectra
together with the emissive lifetimes were measured on Edinburgh FLSꢀ920
fluorescence spectrometer. Emission spectra were recorded by exciting the
samples at their absorption maximum unless otherwise mentioned. All the
experiments in solutions were performed at a concentration of 1 ×10−5 M.
The luminescent quantum yield (ΦPL) in degassed dichloromethane solutions,
powder samples and films at room temperature were determined by the
integrating sphere (142 mm in diameter) using Edinburgh FLSꢀ920
fluorescence spectrometer. Cyclic voltammetry was measured on CHI 660E
electrochemical workstation (Shanghai CH Instruments) in CH2Cl2 solution
using 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the
supporting electrolyte. The experiments were performed at room temperature
at 1 mM concentration with a threeꢀelectrode cell that consisted of a Pt wire
as an auxiliary electrode, a saturated Ag/Ag+ reference electrode and a glassy
graphite working electrode. Ferrocene/ferrocenium (Fc/Fc+) was used as an
internal standard. Thermogravimetric analysis (TGA) was performed under a
continuous nitrogen flow using a TA Instruments Q50 at a heating rate of
Acknowledgements
We are grateful for financial support from the National Natural
Science Foundation of China (Grants 21650110449, U1405252,
21531008, 21601184 and 21473201), the 973 Project from
MSTC (Grant 2014CB845603), the CAS/SAFEA International
Partnership Program for Creative Research Teams, and the
Strategic Priority Research Program of the Chinese Academy of
Sciences (Grant XDB20000000).
10 °C min −1
.
Crystal Structural Determination. Xꢀray singleꢀcrystal diffraction data
were collected on a Bruker D8 Venture diffractometer using IꢁS 3.0
microfocus source MoꢀKα radiation (λ = 0.71073 Å) and PHOTON II CPAD
Notes and references
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Journal of Materials Chemistry C
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DOI: 10.1039/C8TC03270J
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Tetraphosphine-supported PtAu3 cluster complexes display intense phosphorescence with quantum yields
over 90% in doped films. High-efficiency solution-processable OLEDs are successfully achieved with
extremely small EQE roll-off at practical brightness over 1000 cd m-2.
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