Inorganic Chemistry
Article
(
EcoChemie, Utrecht, The Netherlands), run by a PC with NOVA
REFERENCES
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software of the same manufacturer. EIS spectra were recorded in the
1
neutral to the positively charged state.
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2
Photophysical Measurements. Steady-state fluorescence meas-
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equipped with double monochromators and a Hamamatsu R928P
photomultiplier tube as a detector, at room temperature. The solutions
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suitable Schlenk tube and were deoxygenated by bubbling dinitrogen
for 30 min before measurements. The emission intensities have been
normalized to a nominal absorption value of 0.1. Quantum yields have
been determined by a comparison with the emission of [Ru(bpy) ]Cl
in deaerated acetonitrile (Φ = 0.062).
Single-Crystal X-ray Diffraction Analysis. Crystal data for 1:
C H N O Re S , M = 856.85, monoclinic, space group P2 /n (No.
1
1
4
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2
43
̌
́
2
(
21
12
2
8
2
2
r
1
4), a = 10.625(2) Å, b = 20.994(2) Å, c = 11.677(2) Å, β =
3
−3
05.00(2)°, V = 2515.9(7) Å , Z = 4, d = 2.262 g cm , T = 150(2)
calc
3
−1
(
K, crystal size = 0.12 × 0.06 × 0.06 mm , μ = 9.827 mm , λ(Mo Kα)
0.71073 Å. Refinement of 303 parameters on 4431 independent
reflections out of 35617 measured reflections (Rint = 0.1083, R =
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σ
0
0
1
.0624, and 2θmax = 50.0°) led to R = 0.0429 [I > 2σ(I)], wR =
1
2
.0714 (all data), and S = 1.171, with the largest peak and hole of
−3
.060 and −1.440 e Å . Details of data collection and structure
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solution and refinement can be found in the SI. CCDC 976867
contains the crystallographic data for 1. These data can also be
obtained free of charge from The Cambridge Crystallographic Data
Centre.
Computational Details. Ground-state geometries were optimized
by means of DFT calculations. The parameter-free hybrid functional
44
PBE0 was employed along with the standard valence double-ζ
polarized basis set 6-31G(d,p) for carbon, hydrogen, nitrogen, oxygen,
and sulfur. For rhenium, the Stuttgart-Dresden effective core potentials
were employed along with the corresponding valence triple-ζ basis set.
The nature of all of the stationary points was checked by computing
vibrational frequencies. In order to simulate the absorption electronic
spectrum down to 250 nm, the lowest 30 singlet excitation energies
were computed by means of TD-DFT calculations. Calculations were
done also in the presence of solvent (dichloromethane), described by
the polarizable continuum model using the integral equation
1
3
01. (k) Zhou, J.; Whittell, G. R.; Manners, I. Macromolecules 2014, 47,
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45
46
formalism. All of the calculations were done with Gaussian 09.
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ASSOCIATED CONTENT
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Supporting Information
110, 4724−4771.
X-ray crystallographic data of complex 1 in CIF format and
details on the electrochemical, spectroscopic, crystallographic,
(11) (a) Kang, B. S.; Kim, D. H.; Jung, T. S.; Jang, E. K.; Pak, Y.;
Shin, S. C.; Park, D.-S.; Shim, Y.-B. Synth. Met. 1999, 105, 9−12.
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(
(
5, 825−827.
AUTHOR INFORMATION
12) Coppo, P.; Turner, M. L. J. Mater. Chem. 2005, 15, 1123−1133.
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*
13) Zotti, G.; Zecchin, S.; Schiavon, G.; Berlin, A.; Pagani, G.;
Canavesi, A. Chem. Mater. 1995, 7, 2309−2315.
(
(
14) Schmittel, M.; Lin, H. J. Mater. Chem. 2008, 18, 333−343.
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Fax: +390250314405.
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17) Raimondi, A.; Panigati, M.; Maggioni, D.; D’Alfonso, L.;
Notes
Mercandelli, P.; Mussini, P.; D’Alfonso, G. Inorg. Chem. 2012, 51,
966−2975.
18) Panigati, M.; Mauro, M.; Donghi, D.; Mercandelli, P.; Mussini,
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19) Mauro, M.; Quartapelle Procopio, E.; Sun, Y.; Chien, C.-H.;
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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1
(
M.P., P.M., and G.D. thank the Italian Ministero dell’Istruzione,
Universita
009PRAM8L and PRIN-2012A4Z2RY).
̀
e Ricerca, for financial support (Grants PRIN-
Donghi, D.; Panigati, M.; Mercandelli, P.; Mussini, P.; D’Alfonso, G.;
De Cola, L. Adv. Funct. Mater. 2009, 19, 2607−2614.
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dx.doi.org/10.1021/ic501840p | Inorg. Chem. XXXX, XXX, XXX−XXX