Multimetastability in a Spin-Crossover Compound Leading to Different High-Spin-to-Low-Spin Relaxation Dynamics

被引：25

作者：

Craig, Gavin A. ^{[1
]}

Sanchez Costa, Jose ^{[1
]}

Teat, Simon J. ^{[2
]}

Roubeau, Olivier ^{[3
]}

Yufit, Dmitry S. ^{[4
]}

Howard, Judith A. K. ^{[4
]}

Aromi, Guillem ^{[1
]}

机构：

[1] Univ Barcelona, Dept Quim Inorgan, E-08028 Barcelona, Spain

[2] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Adv Light Source, Berkeley, CA 94720 USA

[3] CSIC, ICMA, E-50009 Zaragoza, Spain

[4] Univ Durham, Dept Chem, Durham DH1 3LE, England

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 12期

关键词：

FE(II) COORDINATION-COMPOUNDS; WIDE THERMAL HYSTERESIS; IRON(II) COMPLEX; STATE; TRANSITION; TEMPERATURE; SYSTEM; LIGAND; L=2,6-DI(PYRAZOL-1-YL)PYRIDINE; PHOTOMAGNETISM;

D O I：

10.1021/ic400776x

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The relaxation kinetics of both the thermally trapped and photoinduced high-spin (HS) states of the spin-crossover compound [Fe(H4L)(2)](ClO4)(2)center dot H2O center dot 2(CH3)(2)CO (1) were measured and found to differ significantly. Calorimetry measurements then demonstrated that relaxation of the thermally trapped phase was concurrent with two separate processes, not previously detected as such. Determination of the photogenerated HS structure revealed a new metastable HS state of the system, much closer structurally to the low-spin phase than the thermally trapped one. This difference is proposed as the root of the disparate kinetic behavior, which is proposed to require two processes in the case of the structurally more complex thermally trapped state. Therefore, light irradiation is shown as a mechanism to decouple effectively the structural and magnetic phase transitions that occur in I during the course of its spin crossover.

引用

页码：7203 / 7209

页数：7

共 47 条

[1] Enhanced porosity in a new 3D Hofmann-like network exhibiting humidity sensitive cooperative spin transitions at room temperature [J].

Bartual-Murgui, Carlos ;

Ortega-Villar, Norma A. ;

Shepherd, Helena J. ;

Carmen Munoz, M. ;

Salmon, Lionel ;

Molnar, Gabor ;

Bousseksou, Azzedine ;

Real, Jose Antonio .

JOURNAL OF MATERIALS CHEMISTRY, 2011, 21 (20) :7217-7222

[2] High-spin to low-spin relaxation kinetics in the [Fe(TRIM)2]Cl2 complex [J].

Bonhommeau, S ;

Bréfuel, N ;

Pálfi, VK ;

Molnár, G ;

Zwick, A ;

Salmon, L ;

Tuchagues, JP ;

Costa, JS ;

Létard, JF ;

Paulsen, H ;

Bousseksou, A .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2005, 7 (15) :2909-2914

[3] Molecular spin crossover phenomenon: recent achievements and prospects [J].

Bousseksou, Azzedine ;

Molnar, Gabor ;

Salmon, Lionel ;

Nicolazzi, William .

CHEMICAL SOCIETY REVIEWS, 2011, 40 (06) :3313-3335

[4] Nanoscale Self-Hosting of Molecular Spin-States in the Intermediate Phase of a Spin-Crossover Material [J].

Brefuel, Nicolas ;

Collet, Eric ;

Watanabe, Hiroshi ;

Kojima, Masaaki ;

Matsumoto, Naohide ;

Toupet, Loic ;

Tanaka, Koichiro ;

Tuchagues, Jean-Pierre .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (47) :14060-14068

[5] Concerted Spin Crossover and Symmetry Breaking Yield Three Thermally and One Light-Induced Crystallographic Phases of a Molecular Material [J].

Brefuel, Nicolas ;

Watanabe, Hiroshi ;

Toupet, Loic ;

Come, Jeremy ;

Matsumoto, Naohide ;

Collet, Eric ;

Tanaka, Koichiro ;

Tuchagues, Jean-Pierre .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (49) :9304-9307

[6] Local Coordination Geometry and Spin State in Novel FeII Complexes with 2,6-Bis(pyrazol-3-yl)pyridine-Type Ligands as Controlled by Packing Forces: Structural Correlations [J].

Craig, Gavin A. ;

Sanchez Costa, Jose ;

Roubeau, Olivier ;

Teat, Simon J. ;

Aromi, Guillem .

CHEMISTRY-A EUROPEAN JOURNAL, 2012, 18 (37) :11703-11715

[7] Coupled Crystallographic Order-Disorder and Spin State in a Bistable Molecule: Multiple Transition Dynamics [J].

Craig, Gavin A. ;

Sanchez Costa, Jose ;

Roubeau, Olivier ;

Teat, Simon J. ;

Aromi, Guillem .

CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (11) :3120-3127

[8] Synthesis of a novel heptacoordinated Fe(III) dinuclear complex: experimental and theoretical study of the magnetic properties [J].

Craig, Gavin A. ;

Barrios, Leoni A. ;

Sanchez Costa, Jose ;

Roubeau, Olivier ;

Ruiz, Eliseo ;

Teat, Simon J. ;

Wilson, Chick C. ;

Thomas, Lynne ;

Aromi, Guillem .

DALTON TRANSACTIONS, 2010, 39 (20) :4874-4881

[9] OLEX2: a complete structure solution, refinement and analysis program [J].

Dolomanov, Oleg V. ;

Bourhis, Luc J. ;

Gildea, Richard J. ;

Howard, Judith A. K. ;

Puschmann, Horst .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 2009, 42 :339-341

[10] Iron Spin-Crossover compounds: from fundamental studies to practical applications [J].

Gamez, Patrick ;

Sanchez Costa, Jose ;

Quesada, Manuel ;

Aromi, Guillem .

DALTON TRANSACTIONS, 2009, (38) :7845-7853

← 1 2 3 4 5 →