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An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)(2)(NCS)(2)] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide)

Reaction of nickel(ii) thiocyanate and tert-butyl 5-phenyl-2-pyridyl nitroxide (phpyNO) afforded a 2p–3d–2p heterospin triad [Ni(phpyNO)(2)(NCS)(2)]. The compound crystallizes in the orthorhombic Pbcn space group. The whole molecule is crystallographically independent. The torsion angles around Ni–O...

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Autores principales: Kyoden, Yukiya, Ishida, Takayuki
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9052934/
https://www.ncbi.nlm.nih.gov/pubmed/35493632
http://dx.doi.org/10.1039/d0ra02041a
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author Kyoden, Yukiya
Ishida, Takayuki
author_facet Kyoden, Yukiya
Ishida, Takayuki
author_sort Kyoden, Yukiya
collection PubMed
description Reaction of nickel(ii) thiocyanate and tert-butyl 5-phenyl-2-pyridyl nitroxide (phpyNO) afforded a 2p–3d–2p heterospin triad [Ni(phpyNO)(2)(NCS)(2)]. The compound crystallizes in the orthorhombic Pbcn space group. The whole molecule is crystallographically independent. The torsion angles around Ni–O–N–C(2py) are 26.8(4) and 27.3(4)° at 400 K, indicating appreciable orbital overlaps of the radical π* and nickel(ii) 3d(x(2)−y(2))/3d(z(2)) orbitals. In a low-temperature region, the torsion was enhanced, and the space group changed to monoclinic P2(1)/c with a doubled asymmetric unit volume. The χ(m)T value was practically null below ca. 140 K and, on heating to 400 K, gradually increased and reached 1.30 cm(3) K mol(−1). A van't Hoff analysis suggests a spin transition at T(1/2) = 530(20) K. Density functional theory calculation reproduced ground S(total) = 0 with singlet-triplet gaps of 910 and 1263 K for the 140 K structure, and the gap was reduced to 297 K at 400 K. Consequently, the present compound can be considered as an incomplete spin-crossover material, as a result of T(1/2) located above the experimental temperature window.
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spelling pubmed-90529342022-04-29 An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)(2)(NCS)(2)] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide) Kyoden, Yukiya Ishida, Takayuki RSC Adv Chemistry Reaction of nickel(ii) thiocyanate and tert-butyl 5-phenyl-2-pyridyl nitroxide (phpyNO) afforded a 2p–3d–2p heterospin triad [Ni(phpyNO)(2)(NCS)(2)]. The compound crystallizes in the orthorhombic Pbcn space group. The whole molecule is crystallographically independent. The torsion angles around Ni–O–N–C(2py) are 26.8(4) and 27.3(4)° at 400 K, indicating appreciable orbital overlaps of the radical π* and nickel(ii) 3d(x(2)−y(2))/3d(z(2)) orbitals. In a low-temperature region, the torsion was enhanced, and the space group changed to monoclinic P2(1)/c with a doubled asymmetric unit volume. The χ(m)T value was practically null below ca. 140 K and, on heating to 400 K, gradually increased and reached 1.30 cm(3) K mol(−1). A van't Hoff analysis suggests a spin transition at T(1/2) = 530(20) K. Density functional theory calculation reproduced ground S(total) = 0 with singlet-triplet gaps of 910 and 1263 K for the 140 K structure, and the gap was reduced to 297 K at 400 K. Consequently, the present compound can be considered as an incomplete spin-crossover material, as a result of T(1/2) located above the experimental temperature window. The Royal Society of Chemistry 2020-04-23 /pmc/articles/PMC9052934/ /pubmed/35493632 http://dx.doi.org/10.1039/d0ra02041a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Kyoden, Yukiya
Ishida, Takayuki
An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)(2)(NCS)(2)] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide)
title An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)(2)(NCS)(2)] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide)
title_full An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)(2)(NCS)(2)] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide)
title_fullStr An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)(2)(NCS)(2)] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide)
title_full_unstemmed An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)(2)(NCS)(2)] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide)
title_short An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)(2)(NCS)(2)] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide)
title_sort indication of spin-transition accompanied by an order-disorder structural transformation in [ni(phpyno)(2)(ncs)(2)] (phpyno = tert-butyl 5-phenyl-2-pyridyl nitroxide)
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9052934/
https://www.ncbi.nlm.nih.gov/pubmed/35493632
http://dx.doi.org/10.1039/d0ra02041a
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