Electron Transfer Across Multiple Hydrogen Bonds: The Case of Ureapyrimidinedione-Substituted Vinyl Ruthenium and Osmium Complexes

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2009
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Pichlmaier, Markus
Zabel, Manfred
Zális, Stanislav
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Ruthenium and osmium complexes 2a,b and 3a,b featuring the N-4,6-dioxo-5,5-dibutyl- or the N-4,6-dioxo-5,5-di-(2-propenyl)-1,4,5,6-tetrahydropyrimidin-2-yl-N′(4-ethenylphenyl)-urea ligand dimerize by a self-complementary quadruply hydrogen-bonding donor/donor/acceptor/acceptor (DDAA) motif. We provide evidence that the dimeric structures are maintained in nonpolar solvents and in 0.1 M NBu4PF6/CH2Cl2 supporting electrolyte solution. All complexes are reversibly oxidized in two consecutive two-electron oxidations (ΔE1/2 ≈ 500 mV) without any discernible potential splitting for the oxidation of the individual hydrogen-bridged redox active moieties. IR and UV/vis/NIR spectroelectrochemistry show a one-step conversion of the neutral to the dication without any discernible features of an intermediate monooxidized radical cation. Oxidation-induced IR changes of the NH and CO groups that are involved in hydrogen bonding are restricted to the styryl-bonded urea NH function. IR band assignments are aided by quantum chemical calculations. Our experimental findings clearly show that, at least in the present systems, the ureapyrimidinedione (Upy) DDAA hydrogen-bonding motif does not support electron transfer. The apparent reason is that neither of the hydrogen-bonding functionalities contributes to the occupied frontier levels. This results in nearly degenerate pairs of MOs representing the in-phase and out-of-phase combinations of the individual monomeric building blocks.

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ISO 690PICHLMAIER, Markus, Rainer F. WINTER, Manfred ZABEL, Stanislav ZÁLIS, 2009. Electron Transfer Across Multiple Hydrogen Bonds: The Case of Ureapyrimidinedione-Substituted Vinyl Ruthenium and Osmium Complexes. In: Journal of the American Chemical Society. 2009, 131(13), pp. 4892-4903. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja809566g
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@article{Pichlmaier2009-04-08Elect-13822,
  year={2009},
  doi={10.1021/ja809566g},
  title={Electron Transfer Across Multiple Hydrogen Bonds: The Case of Ureapyrimidinedione-Substituted Vinyl Ruthenium and Osmium Complexes},
  number={13},
  volume={131},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={4892--4903},
  author={Pichlmaier, Markus and Winter, Rainer F. and Zabel, Manfred and Zális, Stanislav}
}
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    <dcterms:abstract xml:lang="eng">Ruthenium and osmium complexes 2a,b and 3a,b featuring the N-4,6-dioxo-5,5-dibutyl- or the N-4,6-dioxo-5,5-di-(2-propenyl)-1,4,5,6-tetrahydropyrimidin-2-yl-N′(4-ethenylphenyl)-urea ligand dimerize by a self-complementary quadruply hydrogen-bonding donor/donor/acceptor/acceptor (DDAA) motif. We provide evidence that the dimeric structures are maintained in nonpolar solvents and in 0.1 M NBu4PF6/CH2Cl2 supporting electrolyte solution. All complexes are reversibly oxidized in two consecutive two-electron oxidations (ΔE1/2 ≈ 500 mV) without any discernible potential splitting for the oxidation of the individual hydrogen-bridged redox active moieties. IR and UV/vis/NIR spectroelectrochemistry show a one-step conversion of the neutral to the dication without any discernible features of an intermediate monooxidized radical cation. Oxidation-induced IR changes of the NH and CO groups that are involved in hydrogen bonding are restricted to the styryl-bonded urea NH function. IR band assignments are aided by quantum chemical calculations. Our experimental findings clearly show that, at least in the present systems, the ureapyrimidinedione (Upy) DDAA hydrogen-bonding motif does not support electron transfer. The apparent reason is that neither of the hydrogen-bonding functionalities contributes to the occupied frontier levels. This results in nearly degenerate pairs of MOs representing the in-phase and out-of-phase combinations of the individual monomeric building blocks.</dcterms:abstract>
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