Electronic Structure Modulation in an Exceptionally Stable Non-Heme Nitrosyl Iron(II) Spin-Crossover Complex

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• 作者：Lucí ; a Piñ ; eiro-Ló ; pez ; Dr. Norma Ortega-Villar ; Prof. Dr. M. Carmen Muñ ; oz ; Dr. G&#225 ; bor Moln&#225 ; r ; Dr. Jordi Cirera ; Prof. Dr. Rafael Moreno-Esparza ; Prof. Dr. Ví ; ctor M. Ugalde-Saldí ; var ; Dr. Azzedine Bousseksou ; Prof. Dr. Eliseo Ruiz and Prof. Dr. José ; A. Real
• 刊名：Chemistry - A European Journal
• 出版年：2016
• 出版时间：August 26, 2016
• 年：2016
• 卷：22
• 期：36
• 页码：12741-12751
• 全文大小：2107K
• ISSN：1521-3765

文摘

The highly stable nitrosyl iron(II) mononuclear complex [Fe(bztpen)(NO)](PF₆)₂ (bztpen=N-benzyl-N,N′,N′-tris(2-pyridylmethyl)ethylenediamine) displays an S=1/2↔S=3/2 spin crossover (SCO) behavior (T_1/2=370 K, ΔH=12.48 kJ mol⁻¹, ΔS=33 J K⁻¹ mol⁻¹) stemming from strong magnetic coupling between the NO radical (S=1/2) and thermally interconverted (S=0↔S=2) ferrous spin states. The crystal structure of this robust complex has been investigated in the temperature range 120–420 K affording a detailed picture of how the electronic distribution of the t_2g–e_g orbitals modulates the structure of the {FeNO}⁷ bond, providing valuable magneto–structural and spectroscopic correlations and DFT analysis.