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2+) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
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2+) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif.
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40
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85052408297
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The C41-C42 bond (1.430(2) Å) is much longer than the bond of C34-C35 (1.356(3) Å), which is probably caused by recovery of the aromaticity of the peripheral benzene ring of naphthalene
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The C41-C42 bond (1.430(2) Å) is much longer than the bond of C34-C35 (1.356(3) Å), which is probably caused by recovery of the aromaticity of the peripheral benzene ring of naphthalene.
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41
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85028172007
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All calculations were performed using the Gaussian 09 program suite Gaussian, Inc.: Wallingford, CT See SI for coordinates and full citation
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The multireference methods other than TD-DFT more properly describe the electronic configurations of the open-shell singlet state of diradicals. However the computational costs of multireference methods are quite high and it is unfeasible for the current study. Nonetheless, TD-DFT methods have been previously shown to be useful in estimating absorption bands of species with diradical character. For latest references, see: c)
-
b) The multireference methods other than TD-DFT more properly describe the electronic configurations of the open-shell singlet state of diradicals. However the computational costs of multireference methods are quite high and it is unfeasible for the current study. Nonetheless, TD-DFT methods have been previously shown to be useful in estimating absorption bands of species with diradical character. For latest references, see: c) M. Li, P. J. Hanway, T R. Albright, A. H. Winter, D L. Phillips, J. Am. Chem. Soc. 2014, 136, 12364
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2+ are open-shell singlets in the gas phase (Table S2, SI). Such a difference between calculation and experimental observations may be ascribed to the counter ion effect. For example, bis(triphenylamine)dications with arylene/vinylene-conjugated bridges were reported to be closed-shell singlets in the solid state but their open-shell singlets have the lowest energy in the gas phase
-
2+ are open-shell singlets in the gas phase (Table S2, SI). Such a difference between calculation and experimental observations may be ascribed to the counter ion effect. For example, bis(triphenylamine)dications with arylene/vinylene-conjugated bridges were reported to be closed-shell singlets in the solid state but their open-shell singlets have the lowest energy in the gas phase. S. Zheng, S. Barlow, C. Risko, T L. Kinnibrugh, V. N Khrustalev, S. C. Jones, M. Y Antipin, N M. Tucker, T V. Timofeeva, V. Coropceanu, J. Brédas, S. R. Marder, J. Am. Chem. Soc. 2006, 128, 1812.
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77950176865
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The singlet diradical character (y) may be estimated experimentally from the measured quantities obtained from one- and two-photon absorption spectra as well as from phosphorescence and EPR peaks
-
The singlet diradical character (y) may be estimated experimentally from the measured quantities obtained from one- and two-photon absorption spectra as well as from phosphorescence and EPR peaks. K. Kamada, K. Ohta, A. Shimizu, T. Kubo, R. Kishi, H. Takahashi, E. Botek, B. Champagne, M. Nakano, J. Phys. Chem. Lett. 2010, 1, 937.
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46
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85028163918
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2+ at the various levels by using the broken-symmetry method did not converge to open-shell singlets (OS) but to closed-shell singlets instead
-
2+ at the various levels by using the broken-symmetry method did not converge to open-shell singlets (OS) but to closed-shell singlets instead.
-
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48
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34347384425
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Spin contamination errors were corrected by an approximate spin-projection method
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