Effects of the anion exchange between I<sup>−</sup> and NCS<sup>−</sup> coordinated to Co<sup>2+</sup>-centered tetrahedra in the organic–inorganic hybrid halides
Mixed-anion compounds provide a unique playground for local coordination engineering due to their heteroleptic coordination around cations. Here, we successfully synthesized novel thiocyanate-containing organic-inorganic hybrid halides (CH<sub>3</sub>NH<sub>3</sub>)<sub>2</sub>Co(NCS)<sub>4</sub> and (CH<sub>3</sub>NH<sub>3</sub>)<sub>3</sub>CoI<sub>4</sub>(NCS) with isolated Co(NCS)<sub>4</sub> tetrahedra and mixed-anion CoI<sub>3</sub>(NCS) tetrahedra, respectively. Together with (CH<sub>3</sub>NH<sub>3</sub>)<sub>2</sub>CoI<sub>4</sub> with CoI<sub>4</sub> tetrahedra, they provide different types of anion-coordination around Co<sup>2+</sup> ions. We compare the magnetic properties of these compounds and discuss the effects of anion exchange between I<sup>-</sup> and NCS<sup>-</sup> using density functional theory calculations.
Authors
- Kotaro Fujii (ORCID: https://orcid.org/0000-0003-3309-9118)
- Takafumi Yamamoto (ORCID: https://orcid.org/0000-0002-7960-1014)
- Rie Ito (ORCID: https://orcid.org/0000-0001-9026-4939)
- Masatomo Yashima (ORCID: https://orcid.org/0000-0001-5406-9183)
- Yuiga Nakamura (ORCID: https://orcid.org/0000-0003-3696-0997)
- S. A. Nikolaev (ORCID: https://orcid.org/0000-0001-7481-1007)
- James R. Neilson (ORCID: https://orcid.org/0000-0001-9282-5752)
- Takuya Ohmi (ORCID: https://orcid.org/0000-0001-9761-134X)
- Masaki Azuma (ORCID: https://orcid.org/0000-0002-8378-321X)
- Iain W. H. Oswald (ORCID: https://orcid.org/0000-0002-5466-0405)
- Kisa Matsushima (ORCID: https://orcid.org/0009-0001-0220-6075)
Institutions
- Kyoto University (JP)
- SPring-8 (JP)
- Japan Synchrotron Radiation Research Institute (JP)
- Kanagawa Industrial Technology Center (JP)
- Colorado State University (US)
Publication Details
- Journal
- Dalton Transactions
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5dt00924c
- Primary Topic
- Inorganic Chemistry and Materials
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Ministry of Education, Culture, Sports, Science and Technology
- Japan Society for the Promotion of Science