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Title: Spin crossover intermediate plateau stabilization in a flexible 2-D Hofmann-type coordination polymer

Authors:
; ; ; ; ;  [1];  [2]
  1. (Sydney)
  2. (
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1130607
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chem. Commun.; Journal Volume: 50; Journal Issue: (29) ; 2014
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Klein, Y. Maximilian, Sciortino, Natasha F., Ragon, Florence, Housecroft, Catherine E., Kepert, Cameron J., Neville, Suzanne M., and U. Basel). Spin crossover intermediate plateau stabilization in a flexible 2-D Hofmann-type coordination polymer. United States: N. p., 2014. Web. doi:10.1039/C4CC01079E.
Klein, Y. Maximilian, Sciortino, Natasha F., Ragon, Florence, Housecroft, Catherine E., Kepert, Cameron J., Neville, Suzanne M., & U. Basel). Spin crossover intermediate plateau stabilization in a flexible 2-D Hofmann-type coordination polymer. United States. doi:10.1039/C4CC01079E.
Klein, Y. Maximilian, Sciortino, Natasha F., Ragon, Florence, Housecroft, Catherine E., Kepert, Cameron J., Neville, Suzanne M., and U. Basel). Tue . "Spin crossover intermediate plateau stabilization in a flexible 2-D Hofmann-type coordination polymer". United States. doi:10.1039/C4CC01079E.
@article{osti_1130607,
title = {Spin crossover intermediate plateau stabilization in a flexible 2-D Hofmann-type coordination polymer},
author = {Klein, Y. Maximilian and Sciortino, Natasha F. and Ragon, Florence and Housecroft, Catherine E. and Kepert, Cameron J. and Neville, Suzanne M. and U. Basel)},
abstractNote = {},
doi = {10.1039/C4CC01079E},
journal = {Chem. Commun.},
number = (29) ; 2014,
volume = 50,
place = {United States},
year = {Tue Aug 19 00:00:00 EDT 2014},
month = {Tue Aug 19 00:00:00 EDT 2014}
}
  • Ambient temperature spin crossover with wide hysteresis has been achieved in 2D Hofmann-type materials, where removal of guest molecules optimises ligand–ligand interactions, resulting in increased cooperativity.
  • New heterobimetallic complexes [Cu{sub x}Ni{sub 1-x}(dadb){center_dot}yH{sub 2}O]{sub n} {l_brace}where dadb=2,5-Diamino-3,6-dichloro-1,4-benzoquinone (1); x=1 (2), 0.5 (4), 0.25 (5), 0.125 (6), 0.0625 (7) and 0 (3); y=2; n=degree of polymerization{r_brace} were synthesized and characterized. Heterobimetallic complexes show normal magnetic moments, whereas, monometallic complexes exhibit magnetic moments less than the value due to spin only. Thermo-gravimetric analysis shows that degradation of the ligand dadb moiety is being controlled by the electronic environment of the Cu(II) ions in preference over Ni(II) in heterobimetallic complexes. Existence of the mixed valency/non-integral oxidation states of copper and nickel metal ions in the complex 4 has been attributedmore » from magnetic moment and ESR spectral results. Solid state dc electrical conductivity of all the complexes was investigated. Monometallic complexes were found to be semiconductors, whereas heterobimetallic coordination polymer 4 was found to exhibit metallic behaviour. Existence of mixed valency/ non-integral oxidation state of metal ions seems to be responsible for the metallic behaviour. - Graphical abstract: Contrast to the semiconductor monometallic complexes 2 and 3, the heterobimetallic complex 4 exhibits metallic behaviour attributed to the mixed valency/non-integral oxidation state of the metal ions concluded from magnetic and ESR spectral studies. Highlights: Black-Right-Pointing-Pointer 1-D coordination compounds of the type Cu{sub x}Ni{sub 1-x}(dadb){center_dot}yH{sub 2}O were synthesized and characterized. Black-Right-Pointing-Pointer Thermal degradation of the complexes provides an indication of long range electronic communication between metal to ligand. Black-Right-Pointing-Pointer On inclusion of Ni(II) into 1-D coordination polymer of Cu(II). (a) Cu(II) and Ni(II) ions exhibit non-integral oxidation state. (b) resulting heterobimetallic complex 4 exhibits metallic behaviour at all temperature range of the present study whereas monometallic complexes are semiconductor.« less
  • Materials that display multiple stepped spin crossover (SCO) transitions with accompanying hysteresis present the opportunity for ternary, quaternary, and quinary electronic switching and data storage but are rare in existence. Herein, we present the first report of a four-step hysteretic SCO framework. Single-crystal structure analysis of a porous 3D Hofmann-like material showed long-range ordering of spin states: HS, HS 0.67LS 0.33, HS 0.5LS 0.5, HS 0.33LS 0.67, and LS. These detailed structural studies provide insight into how multistep SCO materials can be rationally designed through control of host–host and host–guest interactions.