Issue 8, 2024

Fine-tuning of thermally induced SCO behaviors of trinuclear cyanido-bridged complexes by regulating the electron donating ability of CCN-terminal fragments

Abstract

To achieve fine regulation of FeII SCO behavior, a series of trinuclear cyanido-bridged complexes trans-[CpMen(dppe)MII(CN)]2[Fe1II(abpt)2](OTf)2 (1–4) (1, M = Fe2 and n = 1; 2, M = Fe2 and n = 4; 3, M = Fe2 and n = 5; 4, M = Ru and n = 5; CpMen = alkyl cyclopentadienyl with n = 1, 4, 5; dppe = 1,2-bis-(diphenylphosphino)ethane; abpt = 4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole and OTf = CF3SO3) were synthesized and fully characterized by using elemental analysis, X-ray crystallography, magnetic measurements, variable-temperature IR spectroscopy and Mössbauer spectroscopy. It is worth mentioning that different from many mononuclear Fe(abpt)2X2 (X = NCS, NCSe, N(CN)2, C(CN)3, (NC)2CC(OCH3)C(CN)2, (NC)2CC(OC2H5)C(CN)2, C16SO3 and Cl) complexes with more than one polymorph, only one polycrystalline form was found in complexes 1–4. Moreover, the thermally induced SCO behaviors of these four complexes are independent of intermolecular π–π interactions. The electron-donating ability of the CCN-terminal fragment of CpMen(dppe)MIICN can be flexibly regulated by changing the methyl number (n) of the cyclopentadiene ligand or metal ion type (MII). These investigations indicate that the electron-donating ability of the CCN-terminal fragment has an influence on the SCO behavior of Fe1II. The spin transition temperature (T1/2) of the complexes decreases with the increase of the electron-donating ability of the fragment CpMen(dppe)MII. This study provides a new strategy to predict and precisely regulate the behaviors of SCO complexes.

Graphical abstract: Fine-tuning of thermally induced SCO behaviors of trinuclear cyanido-bridged complexes by regulating the electron donating ability of CCN-terminal fragments

Supplementary files

Article information

Article type
Paper
Submitted
17 Dec 2023
Accepted
22 Jan 2024
First published
24 Jan 2024

Dalton Trans., 2024,53, 3777-3784

Fine-tuning of thermally induced SCO behaviors of trinuclear cyanido-bridged complexes by regulating the electron donating ability of CCN-terminal fragments

Y. Huang, Y. He, Y. Liu, J. Fu, X. Liu, X. Wu and T. Sheng, Dalton Trans., 2024, 53, 3777 DOI: 10.1039/D3DT04226J

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