F. M. MacDonnell, M. O. Wolf et al.
Hamamatsu Dynamic Range Streak Camera (excitation source:
EKSPLA PL2241 Nd:YAG laser, lex =355 nm, fwhm=35 ps). Where
wavelengths other than 355 nm were required, an EKSPLA Model
PG401 picosecond optical parametric generator was pumped at 355 nm
by a PL2241 mode-locked laser to produce wavelengths from 420–
680 nm (Signal) and 720–2300 nm (Idler). Electrochemical data were ob-
tained on a CHI620C electrochemical analyzer (CH Instruments, Austin,
TX, USA). A single-compartment, three-electrode electrochemical cell
was used with either a glassy carbon (1.5 mm diameter disk) or platinum
(1.0 mm diameter disk) from Cypress Systems as working electrode. Im-
mediately before use, the electrode was polished to a mirror finish with
wet alumina (Buehler, 0.05 mm), followed by rinsing with Millipore Milli-
Q water and sonication. A Pt wire and a nonleak Ag/AgCl, satd. KCl ref-
erence electrode (Cypress Systems, model EE009) were used as counter
and reference electrodes, respectively. All potentials were measured and
are quoted versus AgjAgCljsatd. KCl reference electrode. All electro-
chemical data were recorded in acetonitrile with 0.1m Bu4NPF6 as sup-
porting electrolyte. Cyclic voltammetry (CV) and differential pulse vol-
tammetry (DPV) were used for the electrochemical characterization of
respective complexes. Transmittance spectroelectrochemical measure-
ments were performed at constant potential in a quartz thin-layer com-
partment containing a platinum minigrid as working electrode. The liquid
thin layer was spectroscopically probed as a function of time by using a
diode array spectrometer (Hewlett–Packard model 8453). The counter
electrode (platinum wire) and the Ag/AgCl reference electrode were
placed in the quartz cuvette near to the thin layer compartment.
with small volumes (2 mL) or H2O, EtOH and Et2O. This product was
used without further purification. Yield: 19 mg (79%). 1H NMR (4+
5 equiv ZnII, 400 MHz, [D3]acetonitrile): d=7.14 (m, 1H), 7.40 (m, 1H),
7.45 (t, J=4.42 Hz, 1H), 7.49 (t, J=4.72 Hz, 1H), 7.70 (m, 2H), 7.87
(ddd, J=8.15, 5.25, 3.35 Hz, 1H), 7.95 (t, 4.26, 1H), 8.05 (m, 1H), 8.13
(m, 1H), 8.19 (t, 1H), 8.27 (m, 1H), 8.35 (d, J=5.48 Hz, 1H), 8.53 (d, J=
9.75 Hz, 1H), 8.64 (dd, J=8.38, 3.50 Hz, 1H), 8.77 (d, J=8.83 Hz, 1H),
8.99 (d, J=4.26 Hz, 1H), 9.37 (d, J=2.74 Hz, 1H), 9.73 (m, 2H),
10.05 ppm (d, J=7.92 Hz, 1H). HR-ESI MS (m/z): [MꢁH]+ calcd for
C72H39N14O2S4Ru: 1358.1294; found: 1358.1323 (ꢁ2.1 ppm).
Acknowledgements
The authors acknowledge the NSERC (M.O.W.), NSF (CHE0911720,
F.M.M.), Robert A. Welch Foundation (Y-1301, F.M.M.), and Mountain
Equipment Co-op (M.B.M.) for support. We thank Dr. Saeid Kamal
(UBC-LASIR) for assistance with TA measurements.
[2] a) J. D. Megiatto, Jr., A. Antoniuk-Pablant, B. D. Sherman, G.
Kodis, M. Gervaldo, T. A. Moore, A. L. Moore, D. Gust, Proc. Natl.
Acad. Sci. USA 2012, 109, 15578–15583; b) L. L. Tinker, N. D.
Sauvage, J. P. Collin, J. C. Chambron, S. Guillerez, C. Coudret, V.
94, 993–1019; d) S. Campagna, G. Denti, S. Serroni, A. Juris, M.
e) M. E. El-Khouly, C. A. Wijesinghe, V. N. Nesterov, M. E. Zandler,
[4] a) G. Kodis, P. A. Liddell, L. de La Garza, A. L. Moore, T. A.
G. F. Moore, I. H. van Stokkum, G. Kodis, P. A. Liddell, M. Gerval-
do, R. van Grondelle, J. T. M. Kennis, D. Gust, T. A. Moore, A. L.
Benniston, A. Harriman, P. Li, P. V. Patel, C. A. Sams, Chem. Eur. J.
saoka, H.-B. Kraatz, M. Muramatsu, S. Ito, Y. Nagasawa, H. Miyasa-
[5] a) J. Hankache, M. Niemi, H. Lemmetyinen, O. S. Wenger, Inorg.
7338–7346; b) S. Ji, W. Wu, W. Wu, P. Song, K. Han, Z. Wang, S.
Morales, G. Accorsi, N. Armaroli, F. Barigelletti, S. J. A. Pope, M. D.
Synthesis: The preparation of ligand L has been previously reported.[8]
Complexes 2 and 3 were prepared according to modified published litera-
ture procedure.[17] Ru(L)2Cl2,[36] [Ru(L)2(1,10-phenanthroline-5,6-dione)]-
A
dipyrido[3,2-a:2’,3’-c]phenazine-11,12-diamine
(dadppz)
(Scheme S1 in the Supporting Information) used in the preparation of 4
were also prepared using modified literature procedures. Complexes 5
and 6 were prepared as described in the literature.[17b,38]
[Ru(L)2ACHTUNGTRENNUNG(dppz)]ACHTUNGTRENNUNG[PF6]2 (2): Complex 2 was purified by silica gel column
chromatography with CH3CN/H2O/KNO3(aq.) (96:3:1) as eluent. Yield:
0.051 g (27%). 1H NMR (400 MHz, [D3]acetonitrile): d=7.13 (dt, J=
5.18, 3.50 Hz, 1H), 7.36–7.41 (m, 1H), 7.44 (t, J=3.35 Hz, 1H), 7.48 (dt,
J=3.27, 1.87 Hz, 1H), 7.61–7.74 (m, 2H), 7.77–7.87 (m, 1H), 7.91–7.95
(m, 1H), 8.02–8.06 (m, 1H), 8.11–8.20 (m, 3H), 8.24–8.28 (m, 1H), 8.49
(dd, J=6.40, 3.35 Hz, 1H), 8.52 (s, 1H), 8.61 (d, J=8.22 Hz, 1H), 8.74
(ddd, J=8.53, 3.65, 0.91 Hz, 1H), 9.31 (d, J=2.13 Hz, 1H), 9.67 ppm (dd,
J=8.22, 1.22 Hz, 1H); 13C NMR (150.92 MHz, [D3]acetonitrile): d=
121.59, 121.65, 124.05, 124.89, 125.30, 125.74, 126.47, 126.84, 127.34,
128.11, 129.19, 130.71, 130.36, 132.08, 133.09, 133.22, 135.38, 136.17,
139.59, 142.31, 142.97, 145.81, 147.8, 150.40, 152.07, 152.30, 152.96, 153.12,
153.81,
C60H36N10O2F6PS4Ru: 1300.0610; found: 1300.0607 (0.2 ppm).
[Ru(L)2A(tpphz)][PF6]2 (3): Complex 3 was obtained as an orange solid,
160.66 ppm.
HR-ESI
MS
(m/z):
[M]+
calcd
for
C
ACHTUNGTRENNUNG
washed with (2 mL) H2O, EtOH and Et2O and used without further puri-
fication. Yield: 17 mg (77%). 1H NMR (3+5 equiv ZnII, 400 MHz,
[D3]acetonitrile): d=7.11 (m, 1H), 7.39 (m, 3H), 7.68 (m, 2H), 7.82 (m,
1H), 7.94 (m, 3H), 8.29 (m, 1H), 8.39 (dd, J=8.22, 4.87 Hz, 1H), 8.50
(m, 1H), 8.60 (d, 1H), 8.75 (m, 1H), 9.37 (d, J=4.87 Hz, 1H), 9.47 (br s,
1H), 9.96 (d, J=7.31 Hz, 1H), 10.23 ppm (d, J=8.53 Hz, 1H); 13C NMR
(3+5 equiv Zn2+
, 100.63 MHz, [D3]acetonitrile): d=123.72, 125.88,
126.90, 127.09, 127.57, 128.25, 128.70, 129.71, 129.91, 131.40, 132.04,
132.24, 135.01, 135.47, 137.22, 138.03, 141.56, 141.78, 143.67, 144.75,
148.44, 149.29, 149.63, 151.61, 152.07, 154.99, 156.38, 158.92, 159.12,
161.62 ppm. HR-ESI MS (m/z): [M]+ calcd for C66H38N12O2F6PS4Ru:
1402.0818; found: 1402.0825 (ꢁ0.5 ppm).
[8] M. B. Majewski, N. R. de Tacconi, F. M. MacDonnell, M. O. Wolf,
[9] S. Singh, N. R. de Tacconi, N. R. G. Diaz, R. O. Lezna, J. MuÇoz Zu-
[Ru(L)2ACHTUNGTRENNUNG(tatpp)]ACHTUNGTRENNUNG[PF6]2 (4): [Ru(L)2(1,10-phenanthroline-5,6-dione)]ACHTNUGTRENUN[GN PF6]2
(20.0 mg, 1.45ꢂ10ꢁ5 mol) was dissolved in CH3CN (15 mL) and added
dropwise to a solution of dadppz (5.5 mg, 1.7ꢂ10ꢁ5 mol, Scheme S1 in
the Supporting Information) in glacial acetic acid/EtOH (1:1, 60 mL)
heated to reflux. The suspension was left heated to reflux for 12 h and
then filtered hot. The filtrate was concentrated to approximately 15 mL
and an aqueous solution of NH4PF6 was added resulting in precipitation
of a dark brown solid. The solid was isolated by filtration and washed
[10] a) J. Fees, M. Ketterle, A. Klein, J. Fiedler, W. Kaim, J. Chem. Soc.
[11] E. J. C. Olson, D. Hu, A. Hçrmann, A. M. Jonkman, M. R. Arkin,
&
10
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ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
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