J. Bonvoisin et al.
FULL PAPER
[3] J. W. Canary, S. Mortezaei, J. A. Liang, Coord. Chem. Rev.
2010, 254, 2249–2266.
[4] M. C. Dul, E. Pardo, R. Lescouezec, Y. Journaux, J. Ferrando-
Soria, R. Ruiz-Garcia, J. Cano, M. Julve, F. Lloret, D. Can-
gussu, C. L. M. Pereira, H. O. Stumpf, J. Pasan, C. Ruiz-Perez,
Coord. Chem. Rev. 2010, 254, 2281–2296.
H 3.7, I 16.9. Mass spectroscopy (FAB, DCM, MNBA) m/z = 773
M+ (calcd. 772.57), 647 [M – I]+, 548 [M – acac-I]+, 423 [M –
Dbm–I]+. IR (KBr): ν = 1509 (C=O), 1598, 1586 and 1482 (C=C),
˜
2923 and 2853 (CH sp3) cm–1. CV (DCM, 0.1 m TBAH, 0.1 Vs–1,
vsSCE) E1/2(RuIII/RuII) = –0.613 V, |ΔE| = 0.073 V, E1/2(RuIII/RuIV
)
=
1.045 V, |ΔE| = 0.074 V. UV/Vis spectroscopy (DCM,
[5] V. A. Friese, D. G. Kurth, Curr. Opin. Colloid Interf. Sci. 2009,
4.92ϫ10–5 m): λ (ε/103 m–1 cm–1) = 562 (2.2), 414 (10.6), 331 (36.7),
257 (27.9), 228 (23.1) nm. 1H NMR (CD2Cl2): δ = 5.32, 12.45 (s, 4
H, Hi), 11.92 (s, 4 H, Hc), 9.83 (t, J = 6.8 Hz, 2 H, Hk), 9.60 (t, J
= 6.8 Hz, 2 H, Ha), 6.55 (d, J = 6.7 Hz, 4 H, Hb), 6.52 (d, J =
6.7 Hz, 4 H, Hj), –1.49 (s, 6 H, Hl), –41.08 (s, 2 H, Hf) ppm. 13C
NMR (CD2Cl2): δ = 53.7, 138.44 (j), 136.86 (b), 123.43 (a), 122.24
(k), 113.08 (d), 109.55 (c), 108.00 (i), 102.54 (h), 6.46 (l) ppm.
14, 81–93.
[6] J. K. H. Hui, M. J. MacLachlan, Coord. Chem. Rev. 2010, 254,
2363–2390.
[7] C. P. Myers, M. E. Williams, Coord. Chem. Rev. 2010, 254,
2416–2428.
[8] C. C. You, R. Dobrawa, C. R. Saha-Moller, F. Würthner, in:
Supermolecular Dye Chemistry, 2005, vol. 258, p. 39–82.
[9] L. Grill, J. Phys. Condens. Matter 2010, 22, 084023.
[10] M. Yu, W. Xu, Y. Benjalal, R. Barattin, E. Laegsgaard, I.
Stensgaard, M. Hliwa, X. Bouju, A. Gourdon, C. Joachim,
T. R. Linderoth, F. Besenbacher, Nano Res. 2009, 2, 254–259.
[11] T. Zambelli, S. Goudeau, J. Lagoute, A. Gourdon, X. Bouju,
S. Gauthier, ChemPhysChem 2006, 7, 1917–1920.
[12] P. J. Low, Dalton Trans. 2005, 2821–2824.
[13] C. J. Villagomez, O. Guillermet, S. Goudeau, F. Ample, H. Xu,
C. Coudret, X. Bouju, T. Zambelli, S. Gauthier, J. Chem. Phys.
2010, 132, 074705.
[Ru(dbm)2(acac-Br)] (6) was also obtained by a direct substitution
on the 3-position of the acac ligand of [Ru(dbm)2(acac)]. [Ru(dbm)2-
(acac)] (2) (0.36 g, 0.55 mmol) was solubilised in dichloromethane,
and the solution was degassed with argon. N-bromosuccinimide
(NBS) (0.1 g, 0.56 mmol) was solubilised in dichloromethane and
was added dropwise to the solution. The mixture was stirred at
room temp. The solution gradually became darker (black with red
gleams). The reaction was stopped after the entire addition of NBS,
and the solution was evaporated to dryness. The crude product was
purified using column chromatography on silica with toluene.
[14] B. Calmettes, S. Nagarajan, A. Gourdon, Y. Benjalal, X.
Bouju, M. Abel, L. Porte, R. Coratger, J. Phys. Chem. C 2009,
113, 21169–21176.
Black crystals were obtained with
a yield of 89% (0.4 g).
C35H28BrO6Ru (725.57): calcd. C 57.9, H 3.9, Br 11.0; found C
57.9, H 3.9, Br 11.0. Mass spectroscopy (FAB, DCM, MNBA) m/z
= 727 M+ (calcd. 725.57), 647 [M – Br]+, 548 [M – acac-Br]+. IR
[15] O. Guillermet, E. Niemi, S. Nagarajan, X. Bouju, D. Martrou,
A. Gourdon, S. Gauthier, Angew. Chem. Int. Ed. 2009, 48,
1970–1973.
[16] C. J. Villagomez, T. Zambelli, S. Gauthier, A. Gourdon, C.
Barthes, S. Stojkovic, C. Joachim, Chem. Phys. Lett. 2007, 450,
107–111.
[17] X. Lu, K. W. Hipps, X. D. Wang, U. Mazur, J. Am. Chem. Soc.
1996, 118, 7197–7202.
[18] M. Lastapis, M. Martin, D. Riedel, L. Hellner, G. Comtet, G.
Dujardin, Science 2005, 308, 1000–1003.
(KBr): ν = 1521 (C=O), 1598, 1586 and 1483 (C=C), 2923 (CH
˜
sp3) cm–1. CV (DCM, 0.1 m TBAH, 0.1 Vs–1, vs. SCE) E1/2(RuIII
/
RuII) = –0.608 V, |ΔE| = 0.074 V, E1/2(RuIII/RuIV) = 1.058 V, |ΔE|
= 0.073 V. UV/Vis spectroscopy (DCM, 5.17ϫ10–5 m): λ (ε/
103 m–1 cm–1) = 556 (2.4), 412 (11.6), 331 (41.0), 258 (30.6), 228
1
(22.8) nm. H NMR (CD2Cl2): δ = 5.32, 12.38 (s, 4 H, Hi), 12.26
(s, 4 H, Hc), 9.79 (t, J = 6.9 Hz, 2 H, Hk), 9.67 (t, J = 6.9 Hz, 2 H,
Ha), 6.62 (d, J = 6.7 Hz, 4 H, Hj), 6.50 (d, J = 6.7 Hz, 4 H, Hb),
–1.76 (s, 6 H, Hl), –40.61 (s, 2 H, Hf) ppm. 13C NMR (CD2Cl2): δ
= 53.7, 138.32 (b), 137.03 (j), 123.57 (a), 122.42 (k), 112.33 (d),
110.15 (c), 107.82 (i), 102.73 (h), –0.05 (l) ppm.
[19] L. Lafferentz, F. Ample, H. Yu, S. Hecht, C. Joachim, L. Grill,
Science 2009, 323, 1193–1197.
[20]
M. S. Alam, M. Stocker, K. Gieb, P. Muller, M. Haryono, K.
Student, A. Grohmann, Angew. Chem. Int. Ed. 2010, 49, 1159–
1163.
S. Guo, S. A. Kandel, J. Phys. Chem. Lett. 2010, 1, 420–424.
Y. H. Lu, R. Quardokus, C. S. Lent, F. Justaud, C. Lapinte,
S. A. Kandel, J. Am. Chem. Soc. 2010, 132, 13519–13524.
Z. Q. Wei, S. Guo, S. A. Kandel, J. Phys. Chem. B 2006, 110,
21846–21849.
K. Petukhov, M. S. Alam, H. Rupp, S. Stromsdorfer, P. Muller,
A. Scheurer, R. W. Saalfrank, J. Kortus, A. Postnikov, M.
Ruben, L. K. Thompson, J. M. Lehn, Coord. Chem. Rev. 2009,
253, 2387–2398.
[21]
[22]
Supporting Information (see footnote on the first page of this arti-
cle): X-ray crystallographic files in CIF format for compounds 1–
4 and 6; ORTEP drawings of 2, 3 and 4; Table of crystallographic
data for 1–4 and 6; Table with selected bond lengths and bond
angles for 1–4 and 6; cyclic voltammetry of 1, 2, 5 and 6 (CH2Cl2,
0.1 m TBAH, 0.1 Vs–1). UV/Vis spectra of complexes 1–3 in
[23]
[24]
1
CH2Cl2. UV/Vis spectra of complexes 1, 2, 5 and 6 in CH2Cl2. H
NMR spectra of complexes 1–3, 5 and 6 in CD2Cl2. 13C NMR
spectra of complexes 1–3, 5 and 6 in CD2Cl2.
[25]
[26]
P. Albores, L. D. Slep, L. S. Eberlin, Y. E. Corilo, M. N. Eber-
lin, G. Benitez, M. E. Vela, R. C. Salvarezza, L. M. Baraldo,
Inorg. Chem. 2009, 48, 11226–11235.
P. R. Andres, R. Lunkwitz, G. R. Pabst, K. Bohn, D. Wouters,
S. Schmatloch, U. S. Schubert, Eur. J. Org. Chem. 2003, 3769–
3776.
Acknowledgments
The authors thank the Centre National de la Recherche Sci-
entifique (CNRS) and the World Premier International (WPI), Ma-
terials Nanoarchitectonics (MANA) program for financial support.
Y. B. and X. B. thank the Agence Nationale pour la Recherche
(ANR), Conception et Simulation (COSINUS) program through
the SAMSON (system for adaptive modeling and simulation of
nano objects) project.
[27]
[28]
A. Carella, C. Coudret, G. Guirado, G. Rapenne, G. Vives, J. P.
Launay, Dalton Trans. 2007, 177–186.
E. Figgemeier, L. Merz, B. A. Hermann, Y. C. Zimmermann,
C. E. Housecroft, H. J. Guntherodt, E. C. Constable, J. Phys.
Chem. B 2003, 107, 1157–1162.
V. Ganesh, V. Lakshminarayanan, J. Phys. Chem. B 2005, 109,
16372–16381.
E. Hubner, N. V. Fischer, F. W. Heinemann, U. Mitra, V. Dre-
mov, P. Muller, N. Burzlaff, Eur. J. Inorg. Chem. 2010, 4100–
4109.
[29]
[30]
[1] D. Astruc, C. Ornelas, J. R. Aranzaes, J. Inorg. Organomet. Po-
[31]
lym. Mater. 2008, 18, 4–17.
L. Latterini, G. Pourtois, C. Moucheron, R. Lazzaroni, J. L.
Bredas, A. Kirsch-De Mesmaeker, F. C. De Schryver, Chem.
Eur. J. 2000, 6, 1331–1336.
[2] V. Balzani, A. Credi, M. Venturi, Chem. Eur. J. 2008, 14, 26–
39.
2704
www.eurjic.org
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 2698–2705