Iridium(iii) Bisterpyridine Complex
A
FULL PAPER
with CH2Cl2/MeOH from 0 to 8%. Compound 7 was obtained as an
orange-red solid in 30% yield (191 mg, 0.20 mmol). 1H NMR
([D6]DMSO, 300 MHz): d=10.25 (s, 1H; NH), 9.20 (d, 3J=5.1 Hz, 2H;
Soc. 2001, 123, 6617–6628; d) H. Imahori, Y. Sekiguchi, Y. Kashiwa-
gi, T. Sato, Y. Araki, O. Ito, H. Yamada, S. Fukuzumi, Chem. Eur. J.
2004, 10, 3184–3196.
3
3
H6), 9.07 (s, 2H; H3’5’), 8.89 (d, J=7.6 Hz, 2H; H3), 8.28 (dd, J=7.6 Hz,
[2]a) T. J. Meyer, Acc. Chem. Res. 1989, 22, 163–170; b) J. H. Alstrum-
Acevedo, M. K. Brennaman, T. J. Mayer, Inorg. Chem. 2005, 44,
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Belser, A. von Zelewsky, M. Frank, F. Vogtle, Inorg. Chem. 1993,
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migni, Inorg. Chem. 2001, 40, 5507–5517; e) C. Chiorboli, S. Fracas-
so, F. Scandola, S. Campagna, S. Serroni, R. Konduri, F. M. Mac-
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T. J. Wadas, H. Hester, R. Schmehl, R. Eisenberg, Inorg. Chem.
2005, 44, 6865–6878.
3J=6.9 Hz, 2H; H4), 8.22 (d, 3J=8.4 Hz, 2H; Ho3), 8.06 (d, 3J=8.5 Hz,
3
3
2H; Hm3), 7.95 (t, J=6.9 Hz, 2H; H5), 7.82 (d, J=8.7 Hz, 2H; Ho4), 7.13
3
3
3
(d, J=8.8 Hz, 4H; Ha), 6.97 (d, J=8.8 Hz, 4H; Hb), 6.74 (d, J=8.8 Hz,
2H; Hm4), 3.73 (s, 6H; CH3); MS (ES): m/z (calcd): 976.11 (976.12)
[M+Na]+, 918.16 (918.15) [MꢀCl]+.
[Ir(tpy-C6H4-NHC(O)-C6H4-N
A
N
mixture of compound 7 (94 mg, 0.098 mmol) and tpy- C6H4-NH2 (5)
(32 mg, 0.099 mmol) in ethylene glycol (30 mL) was sonicated for 20 min.
It was degassed by using three vacuum/argon cycles and was heated from
room temperature to 1608C under argon, at which temperature it re-
mained for 20 min. The solution was allowed to cool to room tempera-
ture and water and a saturated solution of KPF6 were added. The precipi-
tate was filtered off and taken up with acetonitrile. Chromatography on a
silica column (eluted with MeCN/water/KNO3 from 100:0:0 to 100:10:1)
gave an almost pure fraction of the desired product. This fraction was pu-
rified on TLC plates (SiO2, 2020 cm, 0.5 mm) and was eluted with
100:18:1.8 MeCN/water/KNO3. Compound 8 was obtained as a bright
red solid in 42% yield (67 mg, 0.042 mmol). 1H NMR (CD3CN,
400 MHz): d=9.08 (s, 2H; D3’5’), 8.98 (s, 1H; NH), 8.96 (s, 2H; H3’5’),
[3]M. Borgstrçm, N. Shaikh, O. Johansson, M. F. Anderlund, S. Styring,
B. kermark, A. Magnuson, L. Hammarstrçm, J. Am. Chem. Soc.
2005, 127, 17504–17515.
[4]a) K. Ohkubo, H. Kotani, J. Shao, Z. Ou, K. M. Kadish, G. Li, R. K.
Pandey, M. Fujitsuka, O. Ito, H. Imahori, S. Fukuzumi, Angew.
Chem. 2004, 116, 871–874; Angew. Chem. Int. Ed. 2004, 43, 853–
856; b) S. Fukuzumi, H. Kotani, K. Ohkubo, S. Ogo, N. Tkachenko,
H. Lemmetyinen, J. Am. Chem. Soc. 2004, 126, 1600–1601.
[5]a) A. C. Benniston, A. Harriman, P. Y. Li, J. P. Rostron, J. W. Verho-
even, Chem. Commun. 2005, 4520–4522; b) Ohkubo, H. Kotani, S.
Fukuzumi, Chem. Commun. 2005, 4520–4522; c) A. C. Benniston,
A. Harriman, P. Li, J. P. Rostron, H. J. van Ramesdonk, M. M.
Groeneveld, H. Zhang, J. W. Verhoeven, J. Am. Chem. Soc. 2005,
127, 16054–16064; d) J. W. Verhoeven, H. J. van Ramesdonk,
M. M. Groeneveld, A. C. Benniston, A. Harriman, ChemPhysChem
2005, 6, 2551–2560.
3
4
8.72 (td, J=8.6 Hz, J=0.6 Hz, 2H; H3D3), 8.27–8.20 (m, 6H; H4D4Ho3),
8.16 (d, 3J=8.9 Hz, 2H; Hm3), 8.08 (d, 3J=8.8 Hz, 2H; Ho1), 7.84 (d, 3J=
8.9 Hz, 2H; Ho4), 7.74–7.69 (2dd, 3J=11.7 Hz, 4J=0.8 Hz, 4H; H6D6,),
7.53–7.46 (m, 4H; H5D5), 7.21 (d, 3J=9 Hz, 4H; Ha), 6.99 (d, 3J=9.0 Hz,
4H; Hb), 6.89 (d, 3J=9.0 Hz, 2H; Hm1), 6.84 (d, 3J=8.8 Hz, 2H; Hm4),
5.10 (s, 2H; NH2), 3.81 ppm (s, 6H; CH3); MS (ES): m/z (calcd): 390.8
(390.7) [Mꢀ3PF6]3+, 658.8 (658.5) [Mꢀ2PF6]2+
.
[6]E. Baranoff, J.-P. Collin, L. Flamigni, J.-P. Sauvage, Chem. Soc. Rev.
2004, 33, 147–155, and references therein.
[7]I. M. Dixon, J.-P. Collin, J.-P. Sauvage, L. Flamigni, S. Encinas, F.
Barigelletti, Chem. Soc. Rev. 2000, 29, 385–391.
Triad D-Ir-A: Compound D-Ir-A (30 mg, 0.018 mmol) dissolved in
DMAc (2.5 mL) was added to a suspension of compound 3 (prepared
from 50 mg, 0.098 mmol of compound A) in DAMc (1 mL) and a few
drops of pyridine. The mixture was stirred for 4 h at room temperature
under argon. H2O and a saturated solution of KPF6 in water were added.
The precipitate was filtered off and taken up with acetonitrile. The crude
was purified on a silica column eluted with MeCN/H2O/KNO3 from
100:0:0 to 100:9:0.9. Triad D-Ir-A was obtained as an orange-yellow solid
with 45% yield (18 mg, 0.008 mmol). 1H NMR (CD3CN, 400 MHz): d=
9.37 (s, 1H; NHA), 9.14 (s, 2H; H3’5’), 9.11 (s, 2H; D3’5’), 9.01 (s, 1H;
NHD), 8.82–8.74 (m, 4H; H3D3), 8.78 (d, 3J=1.7 Hz, 4H; HA), 8.30 (d,
3J=9.0 Hz, 2H; Ho1), 8.28–8.22 (m, 10H; H4D4Ho3Hm1Ho2), 8.16 (d, 3J=
8.8 Hz, 2H; Hm3), 7.8 (d, 3J=9.0 Hz, 2H; Ho4), 7.75–7.73 (m, 4H; H6D6),
7.66 (d, 3J=8.8 Hz, 2H; HmA), 7.64 (d, 3J=8.7 Hz, 2H; Hm2), 7.53–7.49
(m, 4H; H5D5), 7.34 (d, 3J=8.7 Hz 2H; HoA), 7.19 (d, 3J=9.0 Hz, 4H;
Ha), 6.99 (d, 3J=9.0 Hz, 4H; Hb), 6.83 (d, 3J=8.9 Hz, 2H; Hm4), 3.82 (s,
6H; CH3), 1.42 ppm (s, 9H; tBu); MS (ES): m/z (calcd): 1673.7 (1673)
[MHꢀ3PF6]+.
[8]See, for example: a) G. P. Wiederrecht, M. P. Niemczyk, W. A. Svec,
M. R. Wasielewski, J. Am. Chem. Soc. 1996, 118, 81–88; b) T. Yama-
zaki, I. Yamazaki, A. Osuka, J. Phys. Chem. B 1998, 102, 7858–
7865; c) L. Flamigni, M. R. Johnston, L. Giribabu, Chem. Eur. J.
2002, 8, 3938–3947; d) O. Johansson, M. Borgstrçm, R. Lomoth, M.
Palmblad, J. Bergquist, L. Hammarstrçm, L. Sun, B. kermark,
Inorg. Chem. 2003, 42, 2908–2918.
[9]See, for example: a) T. D. M. Bell, A. Stefan, S. Masuo, T. Vosch, M.
Lor, M. Cotlet, J. Hofkens, S. Bernhardt, K. Müllen, M. van der Au-
weraer, J. W. Verhoeven, F. C. De Schryver, ChemPhysChem 2005,
6, 942–948; b) A. D. Sandanayaka, H. Sasabe, Y. Araki, Y. Furusho,
O. Ito, T. Takata, J. Phys. Chem. A 2004, 108, 5145–5155.
[10]E. Baranoff, I. M. Dixon, J.-P. Collin, J.-P. Sauvage, B. Ventura, L.
Flamigni, Inorg. Chem. 2004, 43, 3057–3066.
[11]J. C. Sheehan, P. A. Cruickshank, G. L. Broshart, J. Org. Chem.
1961, 26, 2525–2528.
[12]A view of the crystal structure of compound 6 is given in the Sup-
porting Information (see Figure S2).
[13]L. Flamigni, B. Ventura, F. Barigelletti, E. Baranoff, J.-P. Collin, J.-P.
Sauvage, Eur. J. Inorg. Chem. 2005, 1312–1318.
Acknowledgements
[14]J. P. Collin, I. M. Dixon, J.-P. Sauvage, J. A. G. Williams, F. Barigel-
letti, L. Flamigni, J. Am. Chem. Soc. 1999, 121, 5009–5016.
[15]W. Leslie, R. A. Poole, P. R. Murray, L. J. Yellowlees, A. Beeby,
J. A. G. Williams, Polyhedron 2004, 23, 2769–2777.
[16]W. Leslie, A. S. Bastanov, J. A. K. Howard, J. A. G. Williams, Dalton
Trans. 2004, 623–631.
We thank CNR of Italy (PM-P04-ISTM-C1/ISOF-M5), CNRS (France),
the Ministero dellꢁIstruzione, dellꢁUniversita’ e della Ricerca of Italy
(FIRB, RBNE019H9K) and COST D31 for financial support. E.B. ac-
knowledges support from the French Ministry of Education. We thank
also Johnson Matthey Inc. for a loan of IrCl3.
[17]For the excitation at 320 nm, the relative absorbance derived from
the molar absorption coefficients of the models are for Ir-D: 40%
on D, 60% on Ir; for D-Ir-A: 30% on D, 60% on Ir, 10% on A.
For the excitation at 357 nm the data are for Ir-A: 50% on A, 50%
on Ir, for D-Ir-A: 40% on A, 45% on Ir, 15% on D.
[18]T. C. Barros, S. Brochsztain, V. G. Toscano, P. B. Filho, M. J. Politi, J.
Photochem. Photobiol. A 1997, 111, 97–104.
[19]G. P. Wiederrecht, M. P. Niemczyk, W. A. Svec, M. A. Wasielewski,
J. Am. Chem. Soc. 1996, 118, 81–88.
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