V. W.-W. Yam et al.
(
7
(
8
400 MHz, acetone, 298 K): d=7.03 (d, J=8.6 Hz, 4H; ꢀNC
.11 (m,12H; ꢀNC ), 7.25 (d, J=16.4 Hz, 2H; ꢀCH=CHꢀ), 7.31–7.35
), 7.43 (d, J=16.4 Hz, 2H; ꢀCH=CHꢀ), 7.58 (d, J=
6
H
4
ꢀ), 7.07–
7.30–7.53 (m, 12H; ꢀNC
ꢀC , ꢀCH=CH-), 7.46–7.53 (m, 20H; ꢀNC
pyridine), 9.06 ppm (s, 2H; bipyridine); MS (positive FAB): m/z: 1444
6
H
4
ꢀ and ꢀC
6
H
5
), 7.30–7.34 (m, 14H; ꢀNC
6
H
4
ꢀ,
6
H
5
6
H
5
6 4
H
ꢀ), 8.04–8.09 (m, 4H; bi-
m, 8H; ꢀNC
6 5
H
+
.7 Hz, 4H; ꢀNC
H
ꢀ), 8.14 (dd, J=8.4, 2.0 Hz, 2H; bipyridine), 8.46 (d,
4 3 2 2
[M] ; elemental analyses calcd for C85H54BrN O Re·CH Cl : C 67.49, H
6
4
J=8.4 Hz, 2H; bipyridine), 8.82 ppm (d, J=2.0 Hz, 2H; bipyridine).
3.69, N 3.66; found: C 67.28, H 3.81, N 3.66.
L2: Following the procedure for the preparation of L1, L2 was prepared
by replacing 4-(diphenylamino)benzaldehyde with 4-(bis(4-(9H-carbazol-
Complex 4: The complex was prepared according to the preparation of
complex 1, except that L1 was replaced by L4 (0.488 g, 0.22 mmol).
1
9
-yl)phenyl)amino)benzaldehyde (0.664 g, 1.1 mmol). Yield: 0.325 g
Yield: 0.318 g (62%). H NMR (400 MHz, CDCl
3
, 298 K): d=6.78–7.04
, -CH=CHꢀ), 7.17–7.22 (m, 22H; ꢀNC
and ꢀC H ), 7.38 (d, J=8.8 Hz, 4H; ꢀNC H ꢀ), 7.60 (s, 4H; ꢀC H ),
1
(
48%). H NMR (400 MHz, CDCl
CH=CHꢀ), 7.24–7.34 (m, 16H, phenyl protons; carbazole), 7.43–7.55
m, 30H, ꢀCH=CHꢀ, ꢀNC ꢀ, carbazole), 7.59 (d, J=8.4 Hz, 4H;
NC H ꢀ), 7.43 (d, J=16.5 Hz, 2H; ꢀCH=CHꢀ), 7.58 (d, J=8.4 Hz, 4H;
3
, 298 K): d=7.11 (d, J=16.4 Hz, 2H;
(m, 82H; ꢀNC
6
H
4
and ꢀC
6
H
5
6
H
4
ꢀ
ꢀ
6
5
6
4
6
5
(
6
H
4
8.02–8.08 (m, 4H; bipyridine), 9.02 ppm (s, 2H; bipyridine); MS (positive
+
ꢀ
FAB):
m/z:
2568
[M] ;
elemental
analyses
calcd
for
6
4
ꢀ
NC H ꢀ), 8.00 (dd, J=8.4, 2.0 Hz, 2H; bipyridine), 8.16 (d, J=7.7 Hz,
C173H118BrN O Re·H O: C 80.38, H 4.68, N 2.17; found: C 80.15, H 4.86,
6
4
4
3
2
8
2
H; carbazole), 8.43 (d, J=8.4 Hz, 2H; bipyridine), 8.78 ppm (d, J=
N 2.35.
.0 Hz, 2H; bipyridine).
Complex 5: The complex was prepared according to the preparation of
L3: Following the procedure for the preparation of L1, L3 was prepared
by replacing 4-(diphenylamino)benzaldehyde with 4-(bis(4-(phenylethy-
complex 1, except that L1 was replaced by L5 (0.555 g, 0.22 mmol).
1
Yield: 0.373 g (65%). H NMR (400 MHz, CDCl
3
, 298 K): d=6.39 (d, J=
ꢀ), 6.65 (d, J=
ꢀ), 7.15–7.23 (m,
4H; ꢀCH=CHꢀ), 7.34–7.37 (m, 4H; ꢀNC H ꢀ), 7.99–8.04 (m, 4H; bipyri-
nyl)phenyl)amino)benzaldehyde (0.521 g, 1.1 mmol). Yield: 0.399 g
8.4 Hz, 8H; ꢀNC
6
H
4
ꢀ), 6.54 (d, J=8.6 Hz, 4H; ꢀNC
ꢀ), 6.84–6.96 (m, 100H; ꢀNC
6 4
H
H
6 4
1
(
73%). H NMR (400 MHz, CDCl
3
,
298 K): d=7.05–7.14 (m, 14H,
8.4 Hz, 8H; ꢀNC
6
H
4
ꢀ
C H , ꢀCH=CHꢀ), 7.21 (d, J=16.3 Hz, 2H; ꢀCH=CHꢀ), 7.32–7.38 (m,
6
5
6
4
+
1
7
2H; ꢀNC
6
H
4
ꢀ and ꢀC
6
H
5
), 7.44–7.54 (m, 20H; ꢀNC
6
H
4
ꢀ and ꢀC
6
H
5
),
dine), 8.99 ppm (s, 2H; bipyridine); MS (positive FAB): m/z: 2869 [M] ;
elemental analyses calcd for C197 Re·CH Cl : C 80.44, H 4.64,
N 1.90; found: C 80.71, H 4.71, N 2.13.
Computational details: Calculations were carried out by using the Gaus-
.98 (dd, J=8.4, 2.0 Hz, 2H; bipyridine), 8.41 (d, J=8.4 Hz, 2H; bipyri-
H
134BrN
4
O
3
2
2
dine), 8.76 ppm (d, J=2.0 Hz, 2H; bipyridine).
L4: Following the procedure for the preparation of L1, L4 was prepared
by replacing 4-(diphenylamino)benzaldehyde with 4-(bis(3’,4’,5’-triphen-
[
36]
sian 09 software package.
complexes 1 and 5 with C
On the basis of the ground state optimized geometries in the gas phase,
Geometry optimization was performed for
[
37]
yl-1,1’:2’,1’’-terphenyl-4-yl)amino)benzaldehyde
(1.137 g,
, 298 K): d=6.77–7.04 (m,
, ꢀCH=CHꢀ), 7.14–7.17 (m, 22H; ꢀNC ꢀ and
C H ), 7.37 (d, J=8.7 Hz, 4H; ꢀNC H ꢀ), 7.60 (s, 4H; ꢀC H ), 7.90–
1.1 mmol).
s
symmetry by using DFT at the PBE0 level.
1
Yield: 0.410 g (37%). H NMR (400 Hz, CDCl
2H; ꢀNC ꢀ, ꢀC
3
[
38]
8
ꢀ
6
H
4
6
H
5
6
H
4
the TDDFT method at the same level associated with the conductor-
[
39]
6
5
6
4
6
5
like polarizable continuum model (CPCM) by using dichloromethane
as the solvent was employed to compute the low-energy singlet–singlet
transitions for the complexes. To investigate the nature of the emissive
state, the unrestricted UPBE0 functional was used to optimize the
lowest-energy triplet state of complex 1 without any symmetry constraint.
Vibrational frequencies were calculated for all stationary points to verify
that each was a minimum on the potential energy surface. For the geome-
try optimization, the Stuttgart effective core potentials (ECPs) and the
7
.93 (m, 2H; bipyridine), 8.38 (d, J=8.4 Hz, 2H; bipyridine), 8.73 ppm
(
s, 2H; bipyridine).
L5: Following the procedure for the preparation of L1, L5 was prepared
by replacing 4-(diphenylamino)benzaldehyde with 4-(bis(3’,4’,5’,6’-tetra-
phenyl-1,1’:2’,1’’-terphenyl-4-yl)amino)benzaldehyde (1.305 g, 1.1 mmol).
1
Yield: 0.643 g (51%). H NMR (400 MHz, CDCl
3
, 298 K): d=6.38 (d,
ꢀ), 6.63 (d, J=
, ꢀCH=CHꢀ), 7.10 (d,
ꢀ), 7.93–
.96 (m, 2H; bipyridine), 8.36 (d, J=8.4 Hz, 2H; bipyridine), 8.71 ppm
s, 2H; bipyridine).
Complex 1: A mixture of L1 (0.153 g, 0.22 mmol) and [Re(CO)
0.101 g, 0.2 mmol) in benzene (30 mL) was heated to reflux for 24 h
8
8
H, 8.5 Hz; ꢀNC
6
H
4
ꢀ), 6.55 (d, J=4H, 8.5 Hz; ꢀNC
6 4
H
[
40]
H, 8.5 Hz; ꢀNC
H
ꢀ), 6.84–6.96 (m, 102H; ꢀC
6 5
H
associated basis set were applied to describe for Re with f-type polari-
6
4
[
41]
J=16.2 Hz, 2H; ꢀCH=CHꢀ), 7.24 (d, J=8.8 Hz, 4H; ꢀNC
6 4
H
zation functions (z=0.869).
For all other atoms, the 6-31G(d) basis
[
42]
set was used with the exception of the carbon and hydrogen atoms on
the R groups in complex 5, where 3-21G basis set was employed. For
7
(
[43]
the TDDFT calculations, the same basis set was used for Re atoms but 6-
5
Br]
3
1G(d) basis set was employed for all other atoms. All DFT and TDDFT
(
calculations were performed with a pruned (99590) grid.
under an argon atmosphere. After cooling down to room temperature,
the mixture was filtered and the filtrate was collected. After removing
the benzene under reduced pressure, the residue was purified by column
chromatography with CHCl
sion of diethyl ether to a concentrated solution of the crude product in
CH Cl gave complex 1 as a deep red powder. Yield: 0.115 g (55%).
H NMR (400 MHz, CDCl
, 298 K): d=6.93 (d, J=16.3 Hz, 2H; ꢀCH=
CHꢀ), 7.04–7.15 (m, 16H; ꢀNC ꢀ and ꢀNC
), 7.23–7.32 (m, 10H;
NC H and ꢀCH=CHꢀ), 7.43 (d, J=16.5 Hz, 2H; ꢀCH=CHꢀ), 7.41 (d,
3
as eluent. Recrystallization by vapor diffu-
Acknowledgements
2
2
1
3
V.W.-W.Y. acknowledges support from the University of Hong Kong
under the URC Strategic Research Theme on New Materials. This work
has been supported by a grant from the Theme-Based Research Scheme
6
H
4
6 5
H
ꢀ
6
5
J=8.7 Hz, 4H; ꢀNC
J=1.6 Hz, 2H; bipyridine); MS (positive FAB): m/z: 1044 [M] ; elemen-
tal analyses calcd for C53 Re·2H O: C 58.88„ H 3.92, N 5.14;
found: C 58.44, H 3.55, N 5.18.
6
H
ꢀ), 8.00–8.06 (m, 4H; bipyridine), 9.02 ppm (d,
4
(
TBRS) of the Research Grants Council of the Hong Kong Special Ad-
+
ministrative Region, China (Project No. T23-713/11). T.Y. and D.P.-K.T.
acknowledge the receipt of Postgraduate Studentships and V.K.-M.A. ac-
knowledges the receipt of a University Postdoctoral Fellowship, both
from the University of Hong Kong. We also thank the Information Tech-
nology Services of the University of Hong Kong for providing computa-
tional resources.
H
38BrN
4
O
3
2
Complex 2: The complex was prepared according to the preparation of
complex 1, except that L1 was replaced by L2 (0.298 g, 0.22 mmol).
1
Yield: 0.208 g (61%). H NMR (400 MHz, CDCl
3
, 298 K): d=7.11 (d, J=
ꢀ, carbazole),
ꢀ, carbazole), 8.07–8.18 (m,
2H; bipyridine, carbazole), 9.09 ppm (s, 2H; bipyridine); MS (positive
1
7
1
6.4 Hz, 2H; ꢀCH=CHꢀ), 7.29–7.37 (m, 16H; ꢀNC
6 4
H
.43–7.60 (m, 34H; ꢀCH=CHꢀ, ꢀNC
H
4
6
[
f) M. A. Baldo, D. F. OꢁBrien, Y. You, A. Shoustikov, S. Sibley,
M. E. Thompson, S. R. Forrest, Nature 1998, 395, 151; g) M. A.
+
FAB):
m/z:
1704
Re·H O·
0.16, H 4.40, N 6.32.
[M] ; elemental
analyses
calcd
for
C
101
H
66BrN
8
O
3
2
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(CH CH ) O: C 70.14, H 4.37, N 6.23; found: C
3
2 2
7
Complex 3: The complex was prepared according to the preparation of
complex 1, except that L1 was replaced by L3 (0.241 g, 0.22 mmol).
1
Yield: 0.225 g (78%). H NMR (400 MHz, CDCl
1
3
, 298 K): d=7.00 (d, J=
ꢀ and ꢀC
),
6.14 Hz, 2H; ꢀCH=CHꢀ), 7.10–7.14 (m, 12H; ꢀNC
H
6 5
H
6
4
&
8
&
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
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