Spin State Chemistry: Modulation of Ligand pKa by Spin State Switching in a [2×2] Iron(II) Grid-Type Complex | Zendy

Sébastien Dhers | Zendy; Abhishake Mondal | Zendy; David Aguilà | Zendy; Juan Antonio Ortega | Zendy; Sergi Vela | Zendy; Pierre Dechambenoit | Zendy; Mathieu Rouzières | Zendy; Jonathan R. Nitschke | Zendy; Rodolphe Clérac | Zendy; JeanMaríe Lehn | Zendy

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Spin State Chemistry: Modulation of Ligand pK_a by Spin State Switching in a [2×2] Iron(II) Grid-Type Complex

Author(s) -

Sébastien Dhers,

Abhishake Mondal,

David Aguilà,

Juan Antonio Ortega,

Sergi Vela,

Pierre Dechambenoit,

Mathieu Rouzières,

Jonathan R. Nitschke,

Rodolphe Clérac,

JeanMaríe Lehn

Publication year - 2018

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/jacs.8b03735

Subject(s) - chemistry , spin (aerodynamics) , spin states , ligand (biochemistry) , modulation (music) , state (computer science) , crystallography , inorganic chemistry , thermodynamics , receptor , physics , biochemistry , algorithm , computer science , acoustics

The iron(II) [2×2] grid complex Fe-8H has been synthesized and characterized. It undergoes spin-crossover (SCO) upon deprotonation of the hydrazine-based terpyridine-like ligand. The deprotonation patterns have been determined by X-ray crystallography and 1 H NMR spectroscopy and discussed in relation to the spin state of the iron(II) centers, which influences greatly the p K a of the ligand. The synthesis of the magnetically silent zinc(II) analogue is also reported, and its (de)protonation behavior has been characterized to serve as a reference for the study of the Fe II grid complexes. DFT computations have also been performed in order to investigate how the successive deprotonation of the bridging ligands affects the SCO behavior within the grid.

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