Iron in a Cage: Fixation of a Fe(II)tpy2 Complex by Fourfold Interlinking

Brandl, Thomas and Johannsen, Sven and Häussinger, Daniel and Suryadevara, Nithin and Prescimone, Alessandro and Bernhard, Stefan and Gruber, Manuel and Ruben, Mario and Berndt, Richard and Mayor, Marcel. (2020) Iron in a Cage: Fixation of a Fe(II)tpy2 Complex by Fourfold Interlinking. Angewandte Chemie International Edition, 59 (37). pp. 15947-15952.

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Abstract The coordination sphere of the Fe(II) terpyridine complex 1 is rigidified by fourfold interlinking of both terpyridine ligands. Profiting from an octa-aldehyde precursor complex, the ideal dimensions of the interlinking structures are determined by reversible Schiff-base formation, before irreversible Wittig olefination provided the rigidified complex. Reversed-phase HPLC enables the isolation of the all-trans isomer of the Fe(II) terpyridine complex 1, which is fully characterized. While temperature independent low-spin states were recorded with superconducting quantum interference device (SQUID) measurements for both, the open precursor 8 and the interlinked complex 1, evidence of the increased rigidity of the ligand sphere in 1 was provided by proton T2 relaxation NMR experiments. The ligand sphere fixation in the macrocyclized complex 1 even reaches a level resisting substantial deformation upon deposition on an Au(111) surface, as demonstrated by its pristine form in a low temperature ultra-high vacuum scanning tunneling microscope experiment.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Molecular Devices and Materials (Mayor)
05 Faculty of Science > Departement Chemie > Chemie > Nuclear Magnetic Resonance (Häussinger)
UniBasel Contributors:Mayor, Marcel and Brandl, Thomas and Prescimone, Alessandro and Häussinger, Daniel
Item Type:Article, refereed
Article Subtype:Research Article
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:07 Feb 2023 10:22
Deposited On:11 Mar 2021 11:23

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