The proton NMR magnetic shieldings of the recently synthesized D3d isomers of methylene-bridged [6]cycloparaphenylene (MB[6]CPP) and [12]cyclophenacene hide in themselves the effect of a global paratropic current around the nanobelts, which is induced by a magnetic field parallel to the main symmetry axis of the molecules. The effect is particularly pronounced for the methylene protons of MB[6]CPP, especially for those facing inside the nanobelt. The small experimental chemical shift difference of only 0.2 ppm is incompatible with the separation of the signals caused by the belt curvature, which, by itself, is calculated to be larger than 1 ppm, with both signals shifted upfield with respect to the position detected for the nanobelt. A careful dissection of the proton magnetic shielding in terms of molecular orbital contributions, has permitted a quantitative assessment of the genuine effect on each different proton caused by a substantial paratropic belt-current, which brings all the signals in nice agreement with the experimental spectra.

Disentangling the Contributions to the Proton Magnetic Shielding in Carbon Nanohoops and Nanobelts: Evidence for a Paratropic Belt-Current

Summa F. F.;Monaco G.;Zanasi R.
2020

Abstract

The proton NMR magnetic shieldings of the recently synthesized D3d isomers of methylene-bridged [6]cycloparaphenylene (MB[6]CPP) and [12]cyclophenacene hide in themselves the effect of a global paratropic current around the nanobelts, which is induced by a magnetic field parallel to the main symmetry axis of the molecules. The effect is particularly pronounced for the methylene protons of MB[6]CPP, especially for those facing inside the nanobelt. The small experimental chemical shift difference of only 0.2 ppm is incompatible with the separation of the signals caused by the belt curvature, which, by itself, is calculated to be larger than 1 ppm, with both signals shifted upfield with respect to the position detected for the nanobelt. A careful dissection of the proton magnetic shielding in terms of molecular orbital contributions, has permitted a quantitative assessment of the genuine effect on each different proton caused by a substantial paratropic belt-current, which brings all the signals in nice agreement with the experimental spectra.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11386/4754535
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