Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands

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We report the synthesis and X-ray structures of four Rh 2 (O 2 Ac) 4 (L Ax ) 2 (OAc = acteate, CH 3 COO - ) paddle-wheel complexes ( C1 - C4 ) with methylthio-modified axial ligands L Ax derived from benzamidine ( L1 ), anilinopyrimidine ( L2 ) or isothiourea ( L3 , L4 ) that are capable of forming N‑H×××O hydrogen bonds to the equatorially bridging acetate ligands. This was done with the aim to suppress dissociation of the axial ligands and to make the complexes amenable to single-molecule conductance measurements in a scanning tunneling microscope break-junction (STM-BJ) setup. The characteristic spectroscopic features (NMR, IR, vis), crystal structures, the hydrogen-bonding motifs and a DFT-based screening of their frontier molecular orbitals are presented. Our calculations suggest that hydrogen-bonding stabilizes axial ligand binding by 20kJ/mol to 30 kJ/mol and that the HOMO of the rhodium paddle-wheels is closer to the Au Fermi level than the LUMO, so that the rhodium paddle-wheels are expected to constitute hole conductors.

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ISO 690MANG, André, Michael LINSEIS, Rainer F. WINTER, 2022. Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands. In: Zeitschrift für anorganische und allgemeine Chemie (ZAAC). Wiley. 2022, 648(23), e202200199. ISSN 0863-1786. eISSN 1521-3749. Available under: doi: 10.1002/zaac.202200199
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@article{Mang2022-11Synth-58277,
  year={2022},
  doi={10.1002/zaac.202200199},
  title={Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands},
  number={23},
  volume={648},
  issn={0863-1786},
  journal={Zeitschrift für anorganische und allgemeine Chemie (ZAAC)},
  author={Mang, André and Linseis, Michael and Winter, Rainer F.},
  note={Article Number: e202200199}
}
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    <dcterms:abstract xml:lang="eng">We report the synthesis and X-ray structures of four Rh 2 (O 2 Ac) 4 (L Ax ) 2 (OAc = acteate, CH 3 COO - ) paddle-wheel complexes ( C1 - C4 ) with methylthio-modified axial ligands L Ax derived from benzamidine ( L1 ), anilinopyrimidine ( L2 ) or isothiourea ( L3 , L4 ) that are capable of forming N‑H×××O hydrogen bonds to the equatorially bridging acetate ligands. This was done with the aim to suppress dissociation of the axial ligands and to make the complexes amenable to single-molecule conductance measurements in a scanning tunneling microscope break-junction (STM-BJ) setup. The characteristic spectroscopic features (NMR, IR, vis), crystal structures, the hydrogen-bonding motifs and a DFT-based screening of their frontier molecular orbitals are presented. Our calculations suggest that hydrogen-bonding stabilizes axial ligand binding by 20kJ/mol to 30 kJ/mol and that the HOMO of the rhodium paddle-wheels is closer to the Au Fermi level than the LUMO, so that the rhodium paddle-wheels are expected to constitute hole conductors.</dcterms:abstract>
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