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Volumn 132, Issue 46, 2010, Pages 16700-16713

Designing multifunctional expanded pyridiniums: Properties of branched and fused head-to-tail bipyridiniums

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTIVITIES; BIPHENYL GROUP; BIPYRIDINIUM; DICATIONIC SPECIES; ELECTRON DENSITIES; ELECTRONIC ABSORPTION; ELECTRONWITHDRAWING; INTRA-MOLECULAR CHARGE TRANSFER; LUMINOPHORES; PYRIDINIUM; PYRIDYL; ROOM TEMPERATURE; SINGLET EXCITED STATE; STOKES SHIFT;

EID: 78649279297     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja108668h     Document Type: Article
Times cited : (63)

References (137)
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    • When performing a bibliometric analysis through the ISI Web of Knowledge, a striking point is the close correlation observed in the evolution over the years of the number of publications (and related citations) dealing with the following topics: "viologen" or "bipyridinium" and "ruthenium bipyridine". Two remarkable inflection points are found around 1980 and 1990. They are ascribable to the launching of two related topics: "water splitting" and "artificial photosynthesis", on the one hand, and "molecular devices" including "molecular machines", on the other; see also ref 3.
    • When performing a bibliometric analysis through the ISI Web of Knowledge, a striking point is the close correlation observed in the evolution over the years of the number of publications (and related citations) dealing with the following topics: "viologen" or "bipyridinium" and "ruthenium bipyridine". Two remarkable inflection points are found around 1980 and 1990. They are ascribable to the launching of two related topics: "water splitting" and "artificial photosynthesis", on the one hand, and "molecular devices" including "molecular machines", on the other; see also ref 3.
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    • For selected references dealing with pyridinium-based solvatochromic dyes, see
    • For selected references dealing with pyridinium-based solvatochromic dyes, see
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    • For purely organic pyridinium-based molecules showing a nonlinear optical (NLO) activity, see for instance
    • For purely organic pyridinium-based molecules showing a nonlinear optical (NLO) activity, see for instance
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    • For inorganic NLO-phores, see, for instance: Acc. Chem. Res. 2006, 39, 383-393
    • Marder, S. R., Perry, J. W., and Schaefer, W. P. Science 1989, 245, 626-628 For inorganic NLO-phores, see, for instance: Coe, B. J. Acc. Chem. Res. 2006, 39, 383-393
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    • There are literally hundreds of examples of papers where pyridinium and/or bipyridinium species act as electron acceptors in photoinduced electron transfer processes. For a few selected early and/or seminal and/or influential contributions involving bipyridiniums, see the following references. Topic of prototypical photochemistry of the ruthenium(II) tris(2,2′-bipyridine) complex with the 1,1′-dimethyl-4,4′-bipyridinium electron-accepting quencher
    • There are literally hundreds of examples of papers where pyridinium and/or bipyridinium species act as electron acceptors in photoinduced electron transfer processes. For a few selected early and/or seminal and/or influential contributions involving bipyridiniums, see the following references. Topic of prototypical photochemistry of the ruthenium(II) tris(2,2′-bipyridine) complex with the 1,1′-dimethyl-4,4′-bipyridinium electron-accepting quencher
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    • Topic of multimolecular systems for hydrogen evolution: Nouv. J. Chim. 1977, 1, 449-451
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    • In;, Ed.; D. Reidel Publishing Co.: Dordrecht, The Netherlands,; pp - 28. Topic of integrated supramolecular functional assemblies devoted to artificial photosynthesis
    • Balzani, V., Moggi, L., and Scandola, F. In Supramolecular Photochemistry; Balzani, V., Ed.; D. Reidel Publishing Co.: Dordrecht, The Netherlands, 1987; pp 1 - 28. Topic of integrated supramolecular functional assemblies devoted to artificial photosynthesis
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    • Balzani, V.1    Moggi, L.2    Scandola, F.3    Balzani, V.4
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    • For selected early works in the field, see
    • For selected early works in the field, see
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    • 2 and R1 = H); see ref 24b.
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    • As an illustration of the effect of direct substitution, one can cite the case of N -(2-pyrimidyl)pyridinium derivatives, which are reversibly one-electron reduced at ca. -0.36 V vs SCE in MeCN, see
    • As an illustration of the effect of direct substitution, one can cite the case of N -(2-pyrimidyl)pyridinium derivatives, which are reversibly one-electron reduced at ca. -0.36 V vs SCE in MeCN, see
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    • The first reduction process related to pyridinium occurs at a potential value that is typically shifted from ca. -1.30 to ca. -0.44 V (vs SCE in MeCN) on going from the N -methylpyridinium monomer to the N -methylviologen (MV) dimer (i.e., "paraquat").
    • The first reduction process related to pyridinium occurs at a potential value that is typically shifted from ca. -1.30 to ca. -0.44 V (vs SCE in MeCN) on going from the N -methylpyridinium monomer to the N -methylviologen (MV) dimer (i.e., "paraquat").
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    • note
    • Me, 9-(biphenyl-4-yl)-2-methyl-benzo[ c ]benzo[1,2]quinolizino[3,4,5,6- ija ][1,6]naphthyridin-2,15-diium.
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    • Evans, D.H.1
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    • Similar assignment also holds for analogous 1 N,2,4,6- tetraarylpyridiniums bearing a (substituted) phenyl group at the 1 N position instead of the pyridyl fragment; see ref 14 and also
    • Similar assignment also holds for analogous 1 N,2,4,6- tetraarylpyridiniums bearing a (substituted) phenyl group at the 1 N position instead of the pyridyl fragment; see ref 14 and also
  • 91
    • 78649251728 scopus 로고    scopus 로고
    • In this context it is worth reminding that the intensity (/energy) of the computed CT transition can be slightly overestimated (/underestimated) when using a TD-DFT approach even in conjunction with a hybrid functional (such as in the present case), see, for instance
    • In this context it is worth reminding that the intensity (/energy) of the computed CT transition can be slightly overestimated (/underestimated) when using a TD-DFT approach even in conjunction with a hybrid functional (such as in the present case), see, for instance
  • 94
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    • Me (Figure 6).
    • Me (Figure 6).
  • 95
    • 78649264343 scopus 로고    scopus 로고
    • In the case of molecule 2F, the HOMO and HOMO-1 are near degenerate so that two very close transitions are computed. The first, very intense of ICT character is computed at 395 nm and the second, less intense corresponding to the HOMO-1 to LUMO excitation is computed at 391 nm. In such a case, it is not excluded that the two transitions could be inverted due to the underestimation of ICT energies at the TD-DFT level. From the comparison with the experimental absorption spectrum (Figure 6), this is apparently the case. In such a case it is not excluded, in agreement with the experimental data, that the emitting state could be the one corresponding to a HOMO-1 to LUMO excitation.
    • In the case of molecule 2F, the HOMO and HOMO-1 are near degenerate so that two very close transitions are computed. The first, very intense of ICT character is computed at 395 nm and the second, less intense corresponding to the HOMO-1 to LUMO excitation is computed at 391 nm. In such a case, it is not excluded that the two transitions could be inverted due to the underestimation of ICT energies at the TD-DFT level. From the comparison with the experimental absorption spectrum (Figure 6), this is apparently the case. In such a case it is not excluded, in agreement with the experimental data, that the emitting state could be the one corresponding to a HOMO-1 to LUMO excitation.
  • 96
    • 78649269301 scopus 로고    scopus 로고
    • Me, computed energies (au) of frontier MOs (Figure 7) are, respectively, the following: -0.137 (a)/-0.133 (b) for the LUMO; -0.278 (c)/-0.251 (d) for the HOMO, and -0.283 (e)/-0.275 (f) for the HOMO-1.
    • Me, computed energies (au) of frontier MOs (Figure 7) are, respectively, the following: -0.137 (a)/-0.133 (b) for the LUMO; -0.278 (c)/-0.251 (d) for the HOMO, and -0.283 (e)/-0.275 (f) for the HOMO-1.
  • 98
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    • In agreement with the observed experimental trends, smaller Stokes shifts (Table S-2, Supporting Information) and structural rearrangements were computed in the case of fused systems with respect to the corresponding branched compounds, confirming the former's greater rigidity. More precisely, structural relaxation in both the singlet and the triplet excited states was computed to be mainly related to the planarization of the aryl substituents with respect to the central pyridinium core and proved to be larger in the case of nonfused architectures. For instance, the root mean square deviations (rmsd) computed between ground and singlet excited state structures for 1B and 1F are 0.23 and 0.11, respectively (and similar results hold for the other compounds).
    • In agreement with the observed experimental trends, smaller Stokes shifts (Table S-2, Supporting Information) and structural rearrangements were computed in the case of fused systems with respect to the corresponding branched compounds, confirming the former's greater rigidity. More precisely, structural relaxation in both the singlet and the triplet excited states was computed to be mainly related to the planarization of the aryl substituents with respect to the central pyridinium core and proved to be larger in the case of nonfused architectures. For instance, the root mean square deviations (rmsd) computed between ground and singlet excited state structures for 1B and 1F are 0.23 and 0.11, respectively (and similar results hold for the other compounds).
  • 99
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    • Me, a bona fide CT emitter. For 2F, on the sole basis of the experimental data, it is not possible to establish whether the π-π* emission essentially originates from a "fused-core" localized or an ICT transition or even exhibits a mixed character; see also ref 43.
    • Me, a bona fide CT emitter. For 2F, on the sole basis of the experimental data, it is not possible to establish whether the π-π* emission essentially originates from a "fused-core" localized or an ICT transition or even exhibits a mixed character; see also ref 43.
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    • 2,4,6-Triarylpyrylium tetrafluoroborate salts were prepared by following a modification of the literature methods reported by Moghimi et al. and Wizinger et al. for the synthesis of other 2,4,6-triarylpyrylium salts, see
    • 2,4,6-Triarylpyrylium tetrafluoroborate salts were prepared by following a modification of the literature methods reported by Moghimi et al. and Wizinger et al. for the synthesis of other 2,4,6-triarylpyrylium salts, see
  • 124
    • 78649277478 scopus 로고    scopus 로고
    • Tri- and tetrabranched pyridiniums were synthesized by following a modification of the literature methods reported by Osterby et al., Kessler et al., and Dimroth et al. for the preparation of N -phenolate-2,4,6- triarylpyridinium betaine dyes, see
    • Tri- and tetrabranched pyridiniums were synthesized by following a modification of the literature methods reported by Osterby et al., Kessler et al., and Dimroth et al. for the preparation of N -phenolate-2,4,6- triarylpyridinium betaine dyes, see
  • 131
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    • Singlet excited states of branched systems have been optimized at the CIS level since they present a more relevant through-space CT character for which the use of structures obtained at the TD-DFT level could be unreliable.
    • Singlet excited states of branched systems have been optimized at the CIS level since they present a more relevant through-space CT character for which the use of structures obtained at the TD-DFT level could be unreliable.


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