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)†
Abstract
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–C2py are 26.8(4) and 27.3(4)° at 400 K, indicating appreciable orbital overlaps of the radical π* and nickel(II) 3dx2−y2/3dz2 orbitals. In a low-temperature region, the torsion was enhanced, and the space group changed to monoclinic P21/c with a doubled asymmetric unit volume. The χmT value was practically null below ca. 140 K and, on heating to 400 K, gradually increased and reached 1.30 cm3 K mol−1. A van't Hoff analysis suggests a spin transition at T1/2 = 530(20) K. Density functional theory calculation reproduced ground Stotal = 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 T1/2 located above the experimental temperature window.
![Graphical abstract: 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)](/en/Image/Get?imageInfo.ImageType=GA&imageInfo.ImageIdentifier.ManuscriptID=D0RA02041A&imageInfo.ImageIdentifier.Year=2020)
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