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

Sébastien Dhers; Abhishake Mondal; David Aguilà; Juan Ramírez; Sergi Vela; Pierre Dechambenoit; Mathieu Rouzières; Jonathan R. Nitschke; Rodolphe Clérac; Jean-Marie Lehn

doi:10.1021/jacs.8b03735

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

Sébastien Dhers
, Abhishake Mondal
, David Aguilà
, Juan Ramírez
, Sergi Vela
, Pierre Dechambenoit
, Mathieu Rouzières
, Jonathan R. Nitschke
, Rodolphe Clérac^*
, Jean-Marie Lehn^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

78 Citations (Scopus)

Abstract

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 ¹H NMR spectroscopy and discussed in relation to the spin state of the iron(II) centers, which influences greatly the pK_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.

Original language	English
Pages (from-to)	8218-8227
Journal	Journal of the American Chemical Society
Volume	140
Issue number	26
Online published	6 Jun 2018
DOIs	https://doi.org/10.1021/jacs.8b03735
Publication status	Published - 5 Jul 2018
Externally published	Yes

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@article{ef6b68fe412f4a4fa5e99ecba0655286,

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

abstract = "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 1H NMR spectroscopy and discussed in relation to the spin state of the iron(II) centers, which influences greatly the pKa 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 FeII 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.",

author = "S{\'e}bastien Dhers and Abhishake Mondal and David Aguil{\`a} and Juan Ram{\'i}rez and Sergi Vela and Pierre Dechambenoit and Mathieu Rouzi{\`e}res and Nitschke, \{Jonathan R.\} and Rodolphe Cl{\'e}rac and Jean-Marie Lehn",

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month = jul,

day = "5",

doi = "10.1021/jacs.8b03735",

language = "English",

volume = "140",

pages = "8218--8227",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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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. / Dhers, Sébastien; Mondal, Abhishake; Aguilà, David et al.
In: Journal of the American Chemical Society, Vol. 140, No. 26, 05.07.2018, p. 8218-8227.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Spin State Chemistry

T2 - Modulation of Ligand pKa by Spin State Switching in a [2×2] Iron(II) Grid-Type Complex

AU - Dhers, Sébastien

AU - Mondal, Abhishake

AU - Aguilà, David

AU - Ramírez, Juan

AU - Vela, Sergi

AU - Dechambenoit, Pierre

AU - Rouzières, Mathieu

AU - Nitschke, Jonathan R.

AU - Clérac, Rodolphe

AU - Lehn, Jean-Marie

PY - 2018/7/5

Y1 - 2018/7/5

N2 - 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 1H NMR spectroscopy and discussed in relation to the spin state of the iron(II) centers, which influences greatly the pKa 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 FeII 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.

AB - 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 1H NMR spectroscopy and discussed in relation to the spin state of the iron(II) centers, which influences greatly the pKa 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 FeII 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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U2 - 10.1021/jacs.8b03735

DO - 10.1021/jacs.8b03735

M3 - RGC 21 - Publication in refereed journal

SN - 0002-7863

VL - 140

SP - 8218

EP - 8227

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 26

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