Substituent Effects on Anion Bonding and Disassembly of Hypervalent Iodine Macrocycles

Abstract

A series of phenylalanine-derived hypervalent iodine-based macrocycles (HIMs) bearing electron donating and withdrawing substituents were prepared. The HIM associations with the anion of tetrabutylammonium chloride (TBA-Cl) were systematically investigated using binding isotherms generated via NMR spectroscopy. The association constants of the resulting I-Cl bond were found to linearly correlate with the electronic substituents via Hammett analysis. Electron-withdrawing substituents strengthened the I–Cl bond and disassembled the macrocycle more readily. In addition, the shifting of HIM carbonyl frequencies obtained by Fourier transform infrared (FTIR) spectroscopy were found to correlate with the binding affinities and provide an alternative predictive methodology to determine HIM disassembly and anion binding affinities.

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BibTeX

@misc{arafin2026substituent,
  title = {{Substituent Effects on Anion Bonding and Disassembly of Hypervalent Iodine Macrocycles}},
  author = {Samsul Arafin and Riya Krishnan and Maximilian S. Kersten and Katherine E. Helme and Sean D. Moran and Kyle N. Plunkett},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010288/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010288/v1},
  note = {CC BY},
}

RIS

TY  - UNPB
TI  - Substituent Effects on Anion Bonding and Disassembly of Hypervalent Iodine Macrocycles
AU  - Samsul Arafin
AU  - Riya Krishnan
AU  - Maximilian S. Kersten
AU  - Katherine E. Helme
AU  - Sean D. Moran
AU  - Kyle N. Plunkett
PY  - 2026
DA  - 2026/10/12
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010288/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010288/v1
AB  - A series of phenylalanine-derived hypervalent iodine-based macrocycles (HIMs) bearing electron donating and withdrawing substituents were prepared. The HIM associations with the anion of tetrabutylammonium chloride (TBA-Cl) were systematically investigated using binding isotherms generated via NMR spectroscopy. The association constants of the resulting I-Cl bond were found to linearly correlate with the electronic substituents via Hammett analysis. Electron-withdrawing substituents strengthened the I–Cl bond and disassembled the macrocycle more readily. In addition, the shifting of HIM carbonyl frequencies obtained by Fourier transform infrared (FTIR) spectroscopy were found to correlate with the binding affinities and provide an alternative predictive methodology to determine HIM disassembly and anion binding affinities.
ER  -

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