Temperature dependence of the spin state and geometry in tricobalt paddlewheel complexes with halide axial ligands
Abstract
Trinuclear cobalt paddlewheel complexes, [Co3(dpa)4X2] (dpa = the anion of 2,2'-dipyridylamine, X = Cl–, Br–, –NCS–, –CN–, (NC)2N–), are known to demonstrate a thermally-induced spin-crossover (SCO). Despite a wealth of structural and magnetic information about such complexes, the role of the axial ligand on the characteristic SCO temperature (T1/2) remains ambiguous. The situation is complicated by the observation that the solid state geometry of the complexes, symmetric or unsymmetric, with respect to the central cobalt ion, also appears to influence the SCO behavior. In order to seek trends in the relationship between the nature of the axial ligand, geometry and magnetic properties, we have prepared the first examples of tricobalt paddlewheel complexes with axial fluorido and iodido ligands, as well as two new chlorido and bromido solvates. Their SCO properties are discussed in the context of an examination of previously reported chlorido and bromido adducts. The main conclusions are: (1) T1/2 values follow the trend I– < Br– ≈ Cl– < F–; (2) while the molecular geometry is predominantly guided by crystal packing for the Cl–, Br– and I– derivatives, the presence of an axial fluoride may favor a more symmetric core; (3) the magnetic characterization of a second examplemore »
- Authors:
-
- Centre National de la Recherche Scientifique (CNRS), Pessac (France). Centre de Recherche en Physique des Plasma (CRPP); Univ. of Bordeaux (France)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Zaragoza (Spain)
- Univ. of Oxford (United Kingdom)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1560410
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 47; Journal Issue: 46; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Srinivasan, Anandi, Wang, Xiaoping, Clérac, Rodolphe, Rouzières, Mathieu, Falvello, Larry R., McGrady, John E., and Hillard, Elizabeth A. Temperature dependence of the spin state and geometry in tricobalt paddlewheel complexes with halide axial ligands. United States: N. p., 2018.
Web. doi:10.1039/C8DT03833C.
Srinivasan, Anandi, Wang, Xiaoping, Clérac, Rodolphe, Rouzières, Mathieu, Falvello, Larry R., McGrady, John E., & Hillard, Elizabeth A. Temperature dependence of the spin state and geometry in tricobalt paddlewheel complexes with halide axial ligands. United States. doi:10.1039/C8DT03833C.
Srinivasan, Anandi, Wang, Xiaoping, Clérac, Rodolphe, Rouzières, Mathieu, Falvello, Larry R., McGrady, John E., and Hillard, Elizabeth A. Thu .
"Temperature dependence of the spin state and geometry in tricobalt paddlewheel complexes with halide axial ligands". United States. doi:10.1039/C8DT03833C. https://www.osti.gov/servlets/purl/1560410.
@article{osti_1560410,
title = {Temperature dependence of the spin state and geometry in tricobalt paddlewheel complexes with halide axial ligands},
author = {Srinivasan, Anandi and Wang, Xiaoping and Clérac, Rodolphe and Rouzières, Mathieu and Falvello, Larry R. and McGrady, John E. and Hillard, Elizabeth A.},
abstractNote = {Trinuclear cobalt paddlewheel complexes, [Co3(dpa)4X2] (dpa = the anion of 2,2'-dipyridylamine, X = Cl–, Br–, –NCS–, –CN–, (NC)2N–), are known to demonstrate a thermally-induced spin-crossover (SCO). Despite a wealth of structural and magnetic information about such complexes, the role of the axial ligand on the characteristic SCO temperature (T1/2) remains ambiguous. The situation is complicated by the observation that the solid state geometry of the complexes, symmetric or unsymmetric, with respect to the central cobalt ion, also appears to influence the SCO behavior. In order to seek trends in the relationship between the nature of the axial ligand, geometry and magnetic properties, we have prepared the first examples of tricobalt paddlewheel complexes with axial fluorido and iodido ligands, as well as two new chlorido and bromido solvates. Their SCO properties are discussed in the context of an examination of previously reported chlorido and bromido adducts. The main conclusions are: (1) T1/2 values follow the trend I– < Br– ≈ Cl– < F–; (2) while the molecular geometry is predominantly guided by crystal packing for the Cl–, Br– and I– derivatives, the presence of an axial fluoride may favor a more symmetric core; (3) the magnetic characterization of a second example of an unsymmetric complex supports the observation that they display dramatically lower T1/2 values than their symmetric analogues; and (4) SCO in crystallographically symmetric compounds apparently occurs without loss of molecular or crystallographic symmetry, while a gradual geometric transformation linking the temperature dependence of quasi-symmetric to unsymmetric in crystallographically unconstrained compounds was found.},
doi = {10.1039/C8DT03833C},
journal = {Dalton Transactions},
number = 46,
volume = 47,
place = {United States},
year = {2018},
month = {11}
}
Figures / Tables:

Works referenced in this record:
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Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds
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Molecular and Electronic Structures by Design: Tuning Symmetrical and Unsymmetrical Linear Trichromium Chains
journal, June 2004
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Effects of Weak Intermolecular Interactions on the Molecular Isomerism of Tricobalt Metal Chains
journal, June 2009
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Linear Tricobalt Compounds with Di(2-pyridyl)amide (dpa) Ligands: Temperature Dependence of the Structural and Magnetic Properties of Symmetrical and Unsymmetrical Forms of Co 3 (dpa) 4 Cl 2 in the Solid State
journal, July 2000
- Clérac, Rodolphe; Cotton, F. Albert; Daniels, Lee M.
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Tuning the Metal−Metal Bonds in the Linear Tricobalt Compound Co 3 (dpa) 4 Cl 2 : Bond-Stretch and Spin-State Isomers
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Works referencing / citing this record:
CCDC 1865590: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
Crystal structure refinement with SHELXL
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
One-dimensional coordination polymers of [Co 3 (dpa) 4 ] 2+ and [MF 6 ] 2− (M = Re IV , Zr IV and Sn IV )
journal, January 2015
- Bulicanu, Vladimir; Pedersen, Kasper S.; Rouzières, Mathieu
- Chemical Communications, Vol. 51, Issue 100
CCDC 1865581: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865585: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865589: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
Linear Tricobalt Compounds with Di-(2-pyridyl)amide (dpa) Ligands: Studies of the Paramagnetic Compound Co 3 (dpa) 4 Cl 2 in Solution
journal, December 1999
- Cotton, F. Albert; Murillo, Carlos A.; Wang, Xiaoping
- Inorganic Chemistry, Vol. 38, Issue 26
Rational Self-Assembly of Tricobalt Extended Metal Atom Chains and [MF 6 ] 2- Building Blocks into One-Dimensional Coordination Polymers : Rational Self-Assembly of Tricobalt Extended Metal Atom Chains and [MF
journal, December 2017
- Cortijo, Miguel; Bulicanu, Vladimir; Pedersen, Kasper S.
- European Journal of Inorganic Chemistry, Vol. 2018, Issue 3-4
CCDC 1877180: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
Molecular and Electronic Structures by Design: Tuning Symmetrical and Unsymmetrical Linear Trichromium Chains
journal, June 2004
- Berry, John F.; Cotton, F. Albert; Lu, Tongbu
- Journal of the American Chemical Society, Vol. 126, Issue 22
Symmetrical and Unsymmetrical Compounds Having a Linear Co 3 6+ Chain Ligated by a Spiral Set of Dipyridyl Anions
journal, October 1997
- Cotton, F. Albert; Daniels, Lee M.
- Journal of the American Chemical Society, Vol. 119, Issue 43
Linear Tricobalt Compounds with Di(2-pyridyl)amide (dpa) Ligands: Temperature Dependence of the Structural and Magnetic Properties of Symmetrical and Unsymmetrical Forms of Co 3 (dpa) 4 Cl 2 in the Solid State
journal, July 2000
- Clérac, Rodolphe; Cotton, F. Albert; Daniels, Lee M.
- Journal of the American Chemical Society, Vol. 122, Issue 26
CCDC 1865593: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865582: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865586: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865577: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
Tuning the Metal−Metal Bonds in the Linear Tricobalt Compound Co 3 (dpa) 4 Cl 2 : Bond-Stretch and Spin-State Isomers
journal, March 2001
- Clérac, Rodolphe; Cotton, F. Albert; Daniels, Lee M.
- Inorganic Chemistry, Vol. 40, Issue 6
Structural and magnetic properties of Co3(dpa)4Br2 †
journal, January 2001
- Clérac, Rodolphe; Cotton, F. Albert; Daniels, Lee M.
- Journal of the Chemical Society, Dalton Transactions, Issue 4
Compounds with Symmetrical Tricobalt Chains Wrapped by Dipyridylamide Ligands and Cyanide or Isothiocyanate Ions as Terminal Ligands
journal, March 2001
- Clérac, Rodolphe; Cotton, F. Albert; Jeffery, Stephen P.
- Inorganic Chemistry, Vol. 40, Issue 6
CCDC 1865580: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
Effects of Weak Intermolecular Interactions on the Molecular Isomerism of Tricobalt Metal Chains
journal, June 2009
- Poulsen, Rasmus D.; Overgaard, Jacob; Schulman, Alexander
- Journal of the American Chemical Society, Vol. 131, Issue 22
CCDC 1865583: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865587: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865591: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865578: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
A Three-State Model for the Polymorphism in Linear Tricobalt Compounds
journal, March 2006
- Pantazis, Dimitrios A.; McGrady, John E.
- Journal of the American Chemical Society, Vol. 128, Issue 12
A multiconfigurational approach to the electronic structure of trichromium extended metal atom chains
journal, January 2017
- Spivak, M.; Arcisauskaite, V.; López, X.
- Dalton Transactions, Vol. 46, Issue 19
CCDC 1865584: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865588: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
CCDC 1865592: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
From Homonuclear Metal String Complexes to Heteronuclear Metal String Complexes: From Homonuclear to Heteronuclear Metal String Complexes
journal, April 2015
- Hua, Shao-An; Cheng, Ming-Chuan; Chen, Chun-hsien
- European Journal of Inorganic Chemistry, Vol. 2015, Issue 15
CCDC 1865579: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre
Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds
journal, September 1999
- Hauser, Andreas; Jeftić, Jelena; Romstedt, Harald
- Coordination Chemistry Reviews, Vol. 190-192
CCDC 1877181: Experimental Crystal Structure Determination
dataset, January 2018
- Srinivasan, Anandi; Wang, Xiaoping; Clérac, Rodolphe
- Cambridge Crystallographic Data Centre