V. Lippolis, J. M. López-de-Luzuriaga et al.
FULL PAPER
MALDI-TOF(–): m/z (%) = 695 [Au(C6Cl5)2]– (100). MALDI-
TOF(+): m/z (%) = 553 [Tl(L2)]+ (100). FTIR (Nujol): ν = 836 and
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Computational Details: For DFT and time-dependent DFT calcula-
tions, the model system of the ligand L1a was optimized at the
DFT level of theory using the TURBOMOLE program package.
For this optimization we used the B3-LYP and BH-LYP function-
als[43] as implemented in TURBOMOLE.[44] The electronic struc-
tures for complexes 1 and 3 were calculated by single-point DFT
calculations on model systems 1a and 3a built up from the X-ray
diffraction results. Calculations were performed without any as-
sumption of symmetry.
[3]
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The excitation energies were obtained at the density functional level
by using the time-dependent approach,[45–49] which is a DFT gener-
alization of the Hartree–Fock linear response (HFLR) or random-
phase approximation (RPA) method.[50]
In all calculations, the Karlsruhe split-valence quality basis sets[51]
augmented with polarization functions[52] were used (SVP). The
Stuttgart effective core potentials in TURBOMOLE were used for
Au and Tl.[53]
Crystallography: The crystals were mounted in inert oil on glass
fibres and transferred to the cold gas stream of an Oxford Diffrac-
tion Xcalibur (for the crystals of complex 1) or a Nonius Kappa
CCD diffractometer (3) equipped with an Oxford Instruments low-
temperature attachment. Data were collected by monochromated
Mo-Kα radiation (λ = 0.71073 Å). Scan type ω and φ. Absorption
corrections based on multiple scans were applied with the program
SADABS (for the crystal structure of complex 1) or SORTAV (3).
The structures were solved by direct methods and refined on F2
using the program SHELXL-97.[54] All non-hydrogen atoms were
anisotropically refined. Hydrogen atoms were included using a ri-
ding model.
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CCDC-805083 (for 1) and -805084 (for 3) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Crystal Data for the Crystal Structure of Complex 1:
C9H12F6N4Se2Tl·CH3CN, Mr = 724.54; orthorhombic, Pbca, a =
8.5981(17) Å, b = 18.510(4) Å, c = 24.425(5) Å, V = 3883.3(13) Å3,
Z = 8, ρcalcd. = 2.479 gcm–3, μ(Mo-Kα) = 12.211 mm–1, R1 =
0.0255, wR2 = 0.0567 for 53764 observed reflections [IϾ2σ(I)].
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Crystal Data for 3: C21H12AuCl10N4Se2Tl, Mr = 1234.10, triclinic,
¯
P1, a = 11.0840(11) Å, b = 11.5294(9) Å, c = 13.6587(14) Å, α =
[20]
[21]
[22]
109.604(6)°, β = 94.018(3)°, γ = 103.448(5)°, V = 1578.2(3) Å3, Z
= 2, ρcalcd. = 2.597 gcm–3, μ(Mo-Kα) = 12.917 mm–1, R1 = 0.0691,
wR2 = 0.1852 for 17919 observed reflections [IϾ2σ(I)].
Supporting Information (see footnote on the first page of this arti-
cle): DFT and TD-DFT results for all model systems using BH-
LYP functional and TZVP basis sets for the case of the free ligand.
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Acknowledgments
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a) E. J. Fernández, J. M. López-de-Luzuriaga, M. Monge,
M. E. Olmos, J. Pérez, A. Laguna, A. A. Mohamed, J. P.
Fackler Jr., J. Am. Chem. Soc. 2003, 125, 2022; b) E. J.
Fernández, J. M. López-de-Luzuriaga, M. Monge, M. Montiel,
M. E. Olmos, J. Pérez, A. Laguna, F. Mendizábal, A. A. Mo-
hamed, J. P. Fackler Jr., Inorg. Chem. 2004, 43, 3573; c) J. M.
López-de-Luzuriaga in Modern Supramolecular Gold Chemis-
This work was supported by the Ministerio de Educación y Ciencia
(MEC), Dirección General de Investigación (DGI)/Fondos
Europeos para el Desarrollo Regional (FEDER) (CTQ2010-20500-
C02-01 and CTQ2010-20500-C02-02). T. L. thanks Ministerio de
Ciencia e Innovación (MICINN) for a grant. M. A. and V. L.
thank the Università degli Studi di Cagliari for financial support.
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www.eurjic.org
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 2288–2297