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Issue 11, 2017
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Effects of electron transfer on the stability of hydrogen bonds

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Abstract

The measurement of the dimerization constants of hydrogen-bonded ruthenium complexes (12, 22, 32) linked by a self-complementary pair of 4-pyridylcarboxylic acid ligands in different redox states is reported. Using a combination of FTIR and UV/vis/NIR spectroscopies, the dimerization constants (KD) of the isovalent, neutral states, 12, 22, 32, were found to range from 75 to 130 M−1G0 = −2.56 to −2.88 kcal mol−1), while the dimerization constants (K2−) of the isovalent, doubly-reduced states, (12)2−, (22)2−, (32)2−, were found to range from 2000 to 2500 M−1G0 = −4.5 to −4.63 kcal mol−1). From the aforementioned values and the comproportionation constant for the mixed-valent dimers, the dimerization constants (KMV) of the mixed-valent, hydrogen-bonded dimers, (12), (22), (32), were found to range from 0.5 × 106 to 1.2 × 106 M−1G0 = −7.78 to −8.31 kcal mol−1). On average, the hydrogen-bonded, mixed-valent states are stabilized by −5.27 (0.04) kcal mol−1 relative to the isovalent, neutral, hydrogen-bonded dimers and −3.47 (0.06) kcal mol−1 relative to the isovalent, dianionic hydrogen bonded dimers. Electron exchange in the mixed valence states imparts significant stability to hydrogen bonding. This is the first quantitative measurement of the strength of hydrogen bonds in the presence and absence of electronic exchange.

Graphical abstract: Effects of electron transfer on the stability of hydrogen bonds

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Publication details

The article was received on 01 Aug 2017, accepted on 30 Aug 2017 and first published on 30 Aug 2017


Article type: Edge Article
DOI: 10.1039/C7SC03361C
Citation: Chem. Sci., 2017,8, 7324-7329
  • Open access: Creative Commons BY license
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    Effects of electron transfer on the stability of hydrogen bonds

    Tyler M. Porter, G. P. Heim and C. P. Kubiak, Chem. Sci., 2017, 8, 7324
    DOI: 10.1039/C7SC03361C

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