(NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system

Roger D. Willett, Carlos J. Gómez-García, B. L. Ramakrishna, Brendan Twamley

Research output: Contribution to journalArticle

  • 32 Citations

Abstract

The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2- dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt) 2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order-disorder type involving one arm of the NBu4+ cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) Å and β = 115.642(3)° with V = 6020.8(11) Å3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) Å and β = 115.073(2)° and V = 5652.1(9) Å3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction. In the high temperature phase, the Ni-S distances between anions are accidentally equal, and the stacks behave as nearly uniform antiferromagnetic chains with nearly equal exchange constants. At the phase transition, a non-uniform compression of the stacks occurs and the magnetic moment drops rapidly, indicating a magnetic dimerization of the stacks. Susceptibility and Cp measurements show an approximate 7°C thermal hysteresis.

LanguageEnglish (US)
Pages2232-2237
Number of pages6
JournalPolyhedron
Volume24
Issue number16-17
DOIs
StatePublished - Nov 17 2005

Fingerprint

Phase Transition
Phase transitions
Temperature
Anions
Negative ions
Order disorder transitions
Dimerization
anions
Nickel
Magnetic moments
Hysteresis
Cations
dimerization
Hot Temperature
Positive ions
Cooling
magnetic moments
hysteresis
nickel
disorders

Keywords

  • Antiferromagnetic chain
  • Bistable behavior
  • Crystal structure
  • Dimerization
  • Nickel dithiolate complex
  • Phase transition

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Willett, R. D., Gómez-García, C. J., Ramakrishna, B. L., & Twamley, B. (2005). (NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system. Polyhedron, 24(16-17), 2232-2237. https://doi.org/10.1016/j.poly.2005.03.088

(NBu4)Ni(mnt)2 : A novel bistable high temperature spin-Peierls-like system. / Willett, Roger D.; Gómez-García, Carlos J.; Ramakrishna, B. L.; Twamley, Brendan.

In: Polyhedron, Vol. 24, No. 16-17, 17.11.2005, p. 2232-2237.

Research output: Contribution to journalArticle

Willett, RD, Gómez-García, CJ, Ramakrishna, BL & Twamley, B 2005, '(NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system' Polyhedron, vol. 24, no. 16-17, pp. 2232-2237. https://doi.org/10.1016/j.poly.2005.03.088
Willett RD, Gómez-García CJ, Ramakrishna BL, Twamley B. (NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system. Polyhedron. 2005 Nov 17;24(16-17):2232-2237. https://doi.org/10.1016/j.poly.2005.03.088
Willett, Roger D. ; Gómez-García, Carlos J. ; Ramakrishna, B. L. ; Twamley, Brendan. / (NBu4)Ni(mnt)2 : A novel bistable high temperature spin-Peierls-like system. In: Polyhedron. 2005 ; Vol. 24, No. 16-17. pp. 2232-2237.
@article{ed761fd97b974d679b71d14357740231,
title = "(NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system",
abstract = "The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2- dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt) 2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order-disorder type involving one arm of the NBu4+ cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) {\AA} and β = 115.642(3)° with V = 6020.8(11) {\AA}3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) {\AA} and β = 115.073(2)° and V = 5652.1(9) {\AA}3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction. In the high temperature phase, the Ni-S distances between anions are accidentally equal, and the stacks behave as nearly uniform antiferromagnetic chains with nearly equal exchange constants. At the phase transition, a non-uniform compression of the stacks occurs and the magnetic moment drops rapidly, indicating a magnetic dimerization of the stacks. Susceptibility and Cp measurements show an approximate 7°C thermal hysteresis.",
keywords = "Antiferromagnetic chain, Bistable behavior, Crystal structure, Dimerization, Nickel dithiolate complex, Phase transition",
author = "Willett, {Roger D.} and G{\'o}mez-Garc{\'i}a, {Carlos J.} and Ramakrishna, {B. L.} and Brendan Twamley",
year = "2005",
month = "11",
day = "17",
doi = "10.1016/j.poly.2005.03.088",
language = "English (US)",
volume = "24",
pages = "2232--2237",
journal = "Polyhedron",
issn = "0277-5387",
publisher = "Elsevier Limited",
number = "16-17",

}

TY - JOUR

T1 - (NBu4)Ni(mnt)2

T2 - Polyhedron

AU - Willett, Roger D.

AU - Gómez-García, Carlos J.

AU - Ramakrishna, B. L.

AU - Twamley, Brendan

PY - 2005/11/17

Y1 - 2005/11/17

N2 - The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2- dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt) 2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order-disorder type involving one arm of the NBu4+ cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) Å and β = 115.642(3)° with V = 6020.8(11) Å3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) Å and β = 115.073(2)° and V = 5652.1(9) Å3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction. In the high temperature phase, the Ni-S distances between anions are accidentally equal, and the stacks behave as nearly uniform antiferromagnetic chains with nearly equal exchange constants. At the phase transition, a non-uniform compression of the stacks occurs and the magnetic moment drops rapidly, indicating a magnetic dimerization of the stacks. Susceptibility and Cp measurements show an approximate 7°C thermal hysteresis.

AB - The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2- dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt) 2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order-disorder type involving one arm of the NBu4+ cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) Å and β = 115.642(3)° with V = 6020.8(11) Å3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) Å and β = 115.073(2)° and V = 5652.1(9) Å3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction. In the high temperature phase, the Ni-S distances between anions are accidentally equal, and the stacks behave as nearly uniform antiferromagnetic chains with nearly equal exchange constants. At the phase transition, a non-uniform compression of the stacks occurs and the magnetic moment drops rapidly, indicating a magnetic dimerization of the stacks. Susceptibility and Cp measurements show an approximate 7°C thermal hysteresis.

KW - Antiferromagnetic chain

KW - Bistable behavior

KW - Crystal structure

KW - Dimerization

KW - Nickel dithiolate complex

KW - Phase transition

UR - http://www.scopus.com/inward/record.url?scp=27744584908&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=27744584908&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2005.03.088

DO - 10.1016/j.poly.2005.03.088

M3 - Article

VL - 24

SP - 2232

EP - 2237

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 16-17

ER -