Spin State Chemistry: Modulation of Ligand pKa by Spin State Switching in a [2x2] Iron(II) Grid-Type Complex

被引：67

作者：

Dhers, Sebastien ^{[1
]}

Mondal, Abhishake ^{[2
,3
,4
]}

Aguila, David ^{[2
,3
]}

Ramirez, Juan ^{[1
]}

Vela, Sergi ^{[5
]}

Dechambenoit, Pierre ^{[2
,3
]}

Rouzieres, Mathieu ^{[2
,3
]}

Nitschke, Jonathan R. ^{[1
,6
]}

Clerac, Rodolphe ^{[2
,3
]}

Lehn, Jean-Marie ^{[1
]}

机构：

[1] Univ Strasbourg, Lab Chim Supramol, ISIS, 8 Allee Gaspard Monge, F-67000 Strasbourg, France

[2] CNRS, CRPP, UMR 5031, F-33600 Pessac, France

[3] Univ Bordeaux, CRPP, UMR 5031, F-33600 Pessac, France

[4] Indian Inst Sci, Solid State & Struct Chem Unit, CV Raman Rd, Bangalore 560012, Karnataka, India

[5] Univ Strasbourg, Lab Chim Quant, CNRS, UMR 7177, 1 Rue Blaise Pascal, F-67008 Strasbourg, France

[6] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 26期

关键词：

PROTONIC MODULATION; COORDINATION ARRAYS; HYDRAZONE LIGANDS; METAL-COMPLEXES; CROSSOVER; TEMPERATURE; BEHAVIOR; INTERCONVERSION; COUNTERANIONS; ARCHITECTURES;

D O I：

10.1021/jacs.8b03735

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The iron(II) [2X2] 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 H-1 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.

引用

页码：8218 / 8227

页数：10

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