Issue 17, 2017

Quasi-1D chains of dinickel lantern complexes and their magnetic properties

Abstract

Four new quasi-1D Ni2-lantern chain complexes of the form [Ni2(SOCR)4(L)] (R = Ph, L = DABCO (1); R = Ph, L = pyz (2); R = CH3, L = DABCO (3); R = CH3, L = pyz (4)) were prepared from the reaction of [Ni2(SOCR)4(EtOH)], R = CH3 or Ph, with the N,N′-donor bridging ligands pyrazine (pyz) or 1,4-diazabicyclo[2.2.2]octane (DABCO). Reaction of [Ni2(tba)4(EtOH)], (tba = thiobenzoate) with the mono-N donor ligand quinuclidine (quin) gave the discrete Ni2-lantern complex [Ni2(tba)4(quin)] (5), whereas reaction with pyridine led to fragmentation of the lantern and formation of the known [Ni(tba)2(py)2] (6). Single-crystal X-ray diffraction reveals 2–4 to be 1D chain complexes comprising DABCO or pyz ligands which bridge the Ni2-lantern units. Complex 5 forms dimers through two equivalent Ni⋯S interactions. The Ni–Ni distances within the Ni2-lanterns are 2.5316(18)–2.595(2) Å for the 1D chain complexes 2–4, and 2.5746(4) Å in the dimeric complex 5, respectively. Comparing the solid state magnetism of 5 to precursor [Ni2(tba)4(EtOH)] demonstrates a change in coupling upon change of capping ligand. Meanwhile, chains 1–4 exhibit magnetic properties consistent with an S = 1 system, due to a mixed valent system where the two Ni centers differ in spin state, while 5 possesses two S = 1 Ni(II) centers. DFT calculations confirm low-spin S = 0 {NiS4} and high-spin S = 1 {NiO4} centers in each lantern. Fits to the magnetic susceptibility data of the chains suggest a weak antiferromagnetic mean field interaction is present that is largely 1-D in nature, though neither pyrazine nor DABCO promote significant magnetic interaction between neighboring Ni2-lanterns.

Graphical abstract: Quasi-1D chains of dinickel lantern complexes and their magnetic properties

Supplementary files

Article information

Article type
Paper
Submitted
01 Des 2016
Accepted
16 Feb 2017
First published
02 Mac 2017

Dalton Trans., 2017,46, 5546-5557

Quasi-1D chains of dinickel lantern complexes and their magnetic properties

A. Nimthong-Roldán, J. L. Guillet, J. McNeely, T. J. Ozumerzifon, M. P. Shores, J. A. Golen, A. L. Rheingold and L. H. Doerrer, Dalton Trans., 2017, 46, 5546 DOI: 10.1039/C6DT04535A

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