Issue 10, 2015

Diazopyridine–Ni(ii) complexes exhibiting intra-chain ferromagnetic interaction after irradiation: formation of magnetic gel

Abstract

Diazopyridine–nickel complexes, 1 and 2, were obtained by mixing di(4-pyridyl)diazomethane, D1py2, with Ni(R-hfpip)2; hfpip = 4-(4-R-phenylimino)-1,1,1,5,5,5-hexafluoro-2-pentanone and R = n-hexyl (1) and n-octyl (2), in a 1 : 1 ratio. The discrete reference complex [Ni(n-hexyl-hfpip)(4NOpy)2] (3) was also prepared. In the tube inversion test and the rheological measurements, the sample (20 mM) of 1 and 2 dissolved in EtOH–20% CH2Cl2 solution showed gelation behavior at −4 °C. In a scanning transmission electron microscopy (STEM) image of the xerogel sample, fibers with widths of 500–700 nm were observed. The Vis-NIR spectrum of the gel sample for 1 showed the typical broad absorption at ∼995 nm due to the octahedral Ni(II) complex, suggesting that the pyridine ligands in D1py2 coordinated to the Ni(II) ion to form the chain structure. Complex 3 showed ferromagnetic interaction with J/kB = 26.7 K between the aminoxyl and the Ni(II) through the pyridine ring. Similarly, the thermal profile of χmol values after irradiation of the gel sample of 1 showed a ferromagnetic interaction between the generated triplet carbenes and the Ni(II) ions and provided a magnetic chain structure. The magnetic correlation length was estimated to be 4–5 units from the maximum value of χmolT (12.7 cm3 K mol−1 at 7 K).

Graphical abstract: Diazopyridine–Ni(ii) complexes exhibiting intra-chain ferromagnetic interaction after irradiation: formation of magnetic gel

Supplementary files

Article information

Article type
Research Article
Submitted
24 ⵢⵓⵏ 2015
Accepted
05 ⵖⵓⵛ 2015
First published
05 ⵖⵓⵛ 2015

Inorg. Chem. Front., 2015,2, 917-926

Author version available

Diazopyridine–Ni(II) complexes exhibiting intra-chain ferromagnetic interaction after irradiation: formation of magnetic gel

K. Mori, R. Eguchi, S. Karasawa and N. Koga, Inorg. Chem. Front., 2015, 2, 917 DOI: 10.1039/C5QI00109A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements