Electronic Control of Spin-Crossover Properties in Four-Coordinate Bis(formazanate) Iron(II) Complexes

Journal of the American Chemical Society
Francesca MiloccoEdwin Otten

Abstract

The transition between spin states in d-block metal complexes has important ramifications for their structure and reactivity, with applications ranging from information storage materials to understanding catalytic activity of metalloenzymes. Tuning the ligand field (ΔO) by steric and/or electronic effects has provided spin-crossover compounds for several transition metals in the periodic table, but this has mostly been limited to coordinatively saturated metal centers in octahedral ligand environments. Spin-crossover complexes with low coordination numbers are much rarer. Here we report a series of four-coordinate, (pseudo)tetrahedral Fe(II) complexes with formazanate ligands and demonstrate how electronic substituent effects can be used to modulate the thermally induced transition between S = 0 and S = 2 spin states in solution. All six compounds undergo spin-crossover in solution with T1/2 above room temperature (300-368 K). While structural analysis by X-ray crystallography shows that the majority of these compounds are low-spin in the solid state (and remain unchanged upon heating), we find that packing effects can override this preference and give rise to either rigorously high-spin (6) or gradual spin-crossover behavior (...Continue Reading

References

Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Apr 11, 2000·Accounts of Chemical Research·D SchröderH Schwarz
Sep 11, 2002·Inorganic Chemistry·Bridey Grant JacobiSeth N Brown
Dec 3, 2002·Science·Gregory J HalderJohn D Cashion
Dec 19, 2002·Journal of the American Chemical Society·David M JenkinsJonas C Peters
Feb 11, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Keisaku NakanoSumio Kaizaki
Apr 11, 2006·Angewandte Chemie·Santiago Alvarez, Jordi Cirera
Apr 10, 2007·Journal of the American Chemical Society·Masayuki NiheiHiroki Oshio
May 10, 2007·Accounts of Chemical Research·Sason ShaikDevesh Kumar
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Mar 12, 2010·Journal of the American Chemical Society·Maria Elisa CrestoniJames M Mayer
Mar 4, 2011·Journal of the American Chemical Society·Jeremiah J ScepaniakJeremy M Smith
Apr 13, 2011·Chemical Society Reviews·Malcolm A Halcrow
Mar 19, 2013·Beilstein Journal of Organic Chemistry·Philipp GütlichYann Garcia
Apr 4, 2013·Journal of the American Chemical Society·Yi-Tong WangHui-Zhong Kou
Aug 27, 2014·Journal of the American Chemical Society·Hsiu-Jung LinJeremy M Smith
Jan 9, 2015·Acta Crystallographica. Section C, Structural Chemistry·George M Sheldrick
Jan 9, 2015·Acta Crystallographica. Section C, Structural Chemistry·Anthony L Spek
Mar 5, 2015·Angewandte Chemie·Gerald Knizia, Johannes E M N Klein
May 20, 2015·Accounts of Chemical Research·Patrick L Holland
Nov 12, 2013·Journal of Chemical Theory and Computation·Gerald Knizia
Mar 1, 2007·Journal of Chemical Theory and Computation·Espen TangenAbhik Ghosh
Apr 15, 2016·Journal of the American Chemical Society·Raquel Travieso-PuenteEdwin Otten
Jul 12, 2016·Chemical Reviews·Roald HoffmannGabriele Manca
Jul 16, 2016·Chemistry : a European Journal·Ryo Ohtani, Shinya Hayami
Oct 7, 2016·Physical Chemistry Chemical Physics : PCCP·S LakhloufiP Guionneau
Jan 10, 2017·Chemical Communications : Chem Comm·Anne K HickeyJeremy M Smith
Aug 19, 2017·Chemical Communications : Chem Comm·Natnaree PhukkaphanDavid J Harding
Oct 25, 2017·Journal of the American Chemical Society·Lianrui Hu, Hui Chen
Jun 21, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Francesca MiloccoEdwin Otten

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Citations

Mar 5, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Rafal KulmaczewskiMalcolm A Halcrow
Jun 17, 2021·ACS Nano·Sven JohannsenRichard Berndt

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

SQUEEZE
SHLELXL
SHELXS
PLATON
Bruker
APEX3

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