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DOI: 10.1039/C7CC08535D
COMMUNICATION
Journal Name
The upconverted fluorescence lifetime of IrCIr at 386
was much longer than that of the other three complexes
Figure S17). This is likely related to its short triplet excited
ꢁ
s, 3.
Q. Zhao, C. Huang and F. Li, Chem. Soc. Rev., 2011, 40,
508-2524.
Y. Lu, R. Conway-Kenny, B. Twamley, N. McGoldrick, J.
Zhao, S. M. Draper, ChemPhotoChem., 2017, 1, 544-552.
T. N. Singh-Rachford and F. N. Castellano, Coord. Chem.
Rev. , 2010, 254, 2560-2573.
C. Fan, W. Wu, J. J. Chruma, J. Zhao and C. Yang, J. Am.
Chem. Soc. , 2016, 138, 15405-15412.
Y. Lu, J. Wang, N. McGoldrick, X. Cui, J. Zhao, C. Caverly, B.
Twamley, G. M. Ó Máille, B. Irwin, R. Conway-Kenny and
S. M. Draper, Angew. Chem. Int. ed. , 2016, 128, 14908-
2
4
5
6
7
.
.
.
.
(
lifetime, and consequently less efficient TTET.
a
Table 3. Triplet state properties of the generated complexes.
b
c
d
−1
e
6
−1 −1
f
g
τ
T
(μs)
τ
DF (μs)
K
SV (M )
4448
k
q
(10 M s )
3706
Φ
UC (%)
ꢀ
Φ (%)
RuCRu
RuC
1.2
1.2
0.4
0.9
252
284
386
301
21.6
19.1
15.3
19.0
83.3
56.3
67.2
54.1
4477
3197
IrCIr
IrC
2102
5255
4809
5343
1
4912.
a
−5
b
3
Results of complexes in CH CN solution (1 × 10 M), 298 K. Triplet-state lifetime
c
d
8.
9.
Y. Lu, N. McGoldrick, F. Murphy, B. Twamley, X. Cui, C.
Delaney, G. M. Ó. Máille, J. Wang, J. Zhao and S. M.
Draper, Chem. Eur. J. , 2016, 22, 11349-11356.
2
under N . Upconverted luminance lifetime, called delayed fluorescence. Quenching
e
f
constant. Bimolecular quenching constant. TTA-UC quantum yield under N
2
, with
29 g
BODIPY as a standard (Φ
f
= 71.2% in CH
3
CN).
Singlet oxygen quenching quantum
3
0
yield with Ru(bpy) [2PF ] as a standard (Φ
3
6
ꢀ
= 57.1% in CH
3
CN), at 298 K.
T. F. Schulze and T. W. Schmidt, Energ. Environ. Sci. ,
2
015, 8, 103-125.
1
1
1
0.
Z. Mahmood, A. Toffoletti, J. Zhao and A. Barbon, J.
Lumin. , 2017, 183, 507-512.
J. Zhao, W. Wu, J. Sun and S. Guo, Chem. Soc. Rev., 2013,
The singlet oxygen quenching quantum yield of each
complex was also measured (Figure 4d). Compared to the
mononuclear complexes, the carbazole-bridged dinuclear
complexes, RuCRu and IrCIr, showed considerably higher and
1.
2.
4
2, 5323-5351.
A. El-ghayoury, A. Harriman, A. Khatyr and R. Ziessel, J.
Phys. Chem. A, 2000, 104, 1512-1523.
A. Harriman, A. Khatyr and R. Ziessel, Dalton Trans., 2003,
0, 2061-2068.
desirable singlet oxygen quenching quantum yields (
for RuCRu = 67.2% for IrCIr).
In conclusion, N-substituted carbazole complexes of the d
Φ
ꢀ
= 83.3%
;
Φ
ꢀ
13.
6
transition metals, Ru(II) and Ir(III), were synthesised. The 14.
A. Harriman and R. Ziessel, in Carbon-Rich Compounds,
Wiley-VCH Verlag GmbH & Co. KGaA, 2006, ch2, pp.26-89.
A. Harriman, A. Mayeux, C. Stroh and R. Ziessel, Dalton
Trans. , 2005, 0, 2925-2932.
dinuclear complexes, in which a carbazole moiety is used to
1
5.
generate a conjugated bridging ligand, showed enhanced
absorption in the visible region. The attached carbazole moiety
3
3
16.
X. Cui, J. Zhao, Z. Mohmood and C. Zhang, Chem. Rec. ,
gave rise to the mixed MLCT and ILCT character of the
excited states in these complexes. As postulated, the
combined effects of two metal centres resulted in significantly
improved singlet oxygen quenching quantum yields, when
compared to the mononuclear analogues. Although
measurements on bimetallic complexes such as these are rare
2
016, 16, 173-188.
1
1
7.
8.
W. Wu, J. Zhao, J. Sun, L. Huang and X. Yi, J. Mater. Chem.
C, 2013, 1, 705-716.
S. Goswami, R. W. Winkel, E. Alarousu, I. Ghiviriga, O. F.
Mohammed and K. S. Schanze, J. Phys. Chem. A, 2014,
118, 11735-11743.
they are showing some consistent messages. They are giving 19.
W. Wu, J. Zhao, H. Guo, J. Sun, S. Ji and Z. Wang, Chem.
Eur. J. , 2012, 18, 1961-1968.
some conclusive insight into the potential improvements
6
2
2
2
2
2
0.
1.
2.
3.
4.
J. Wang, Y. Lu, N. McGoldrick, C. Zhang, W. Yang, J. Zhao
and S. M. Draper, J. Mater. Chem. C, 2016, 4, 6131-6139.
S. Q. Fan, C. Kim, B. Fang, K. X. Liao, G. J. Yang, C. J. Li, J. J.
Kim and J. Ko, J. Phys. Chem. C, 2011, 115, 7747-7754.
W. Wu, J. Sun, X. Cui and J. Zhao, J. Mater. Chem. C, 2013,
possible through the use of multinuclear d complexes towards
the practical industrial applications of triplet photosensitisers
for TTA-UC technologies and operations.
We thank Drs J. O'Brien, M. Reuther, M. Feeney and G.
Hessman for spectroscopic and technical assistance. We thank
Prof. J. Zhao for generously facilitating the spectroscopic
measurements in Dalian University of Technology. This
material is based upon works supported by the Science
1
, 4577-4589.
H.-J. Nie, W.-W. Yang, R.-H. Zheng, Q. Shi, H. Chen, J. Yao
and Y.-W. Zhong, Inorg. Chem. , 2015, 54, 1272-1282.
S. R. Salpage, A. Paul, B. Som, T. Banerjee, K. Hanson, M.
D. Smith, A. K. Vannucci and L. S. Shimizu, Dalton Trans. ,
2016, 45, 9601-9607.
Foundation
Ireland
under
Research
Grant
No.
SFI/15/TIDA/2952, SFI/15/1A/3046 and SFI/IACA/3413. Y.L.
and R.C-K. acknowledge PG studentships from the School of 25.
Chemistry, and J.W. from the Irish Research Council. There are
M. Zhou and J. Roovers, Macromolecules, 2001, 34, 244-
2
52.
2
2
2
2
3
6.
7.
8.
9.
0.
J. B. Flanagan, S. Margel, A. J. Bard and F. C. Anson, J. Am.
Chem. Soc., 1978, 100, 4248-4253.
T. Yu, Y. Zeng, J. Chen, Y.-Y. Li, G. Yang and Y. Li, Angew.
Chem. Int. Ed. , 2013, 52, 5631-5635.
no conflicts of interest to declare.
Notes and references
J. Sun, F. Zhong, X. Yi and J. Zhao, Inorg. Chem., 2013, 52,
1.
S. Campagna, F. Puntoriero, F. Nastasi, G. Bergamini and
V. Balzani, in Photochemistry and Photophysics of
Coordination Compounds I, Springer Berlin Heidelberg,
6
299-6310.
W. Wu, H. Guo, W. Wu, S. Ji and J. Zhao, J. Organ. Chem. ,
011, 76, 7056-7064.
2
2007, vol. 280, ch. 133, pp. 117-214.
L. Huang, J. Zhao, S. Guo, C. Zhang and J. Ma, J. Organ.
Chem. , 2013, 78, 5627-5637.
2.
Y. J. Yuan, J. Y. Zhang, Z. T. Yu, J. Y. Feng, W. J. Luo, J. H. Ye
and Z. G. Zou, Inorg. Chem. , 2012, 51, 4123-4133.
4
| J. Name., 2012, 00, 1-3
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