Cyclic Heterometallic Interactions formed from a Flexible Tripeptide Complex Showing Effective Antiferromagnetic Spin Coupling

Developing tunable motifs for heterometallic interactions should be beneficial for fabricating functional materials based on cooperative electronic communications between metal centers. Reported here is the efficient formation of cyclic heterometallic interactions from a complex containing an artifi...

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Bibliographic Details
Published in:Angewandte Chemie 2021-03, Vol.133 (10), p.5239-5243
Main Authors: Miyake, Ryosuke, Suganuma, Eri, Kimura, Shun, Mori, Hirotoshi, Okabayashi, Jun, Kusamoto, Tetsuro
Format: Article
Language:English
Subjects:
Absorption spectroscopy
Antiferromagnetism
Binding sites
Chains
Chemistry
Crystallization
Functional materials
heterometallic complexes
Low temperature
Magnetic measurement
Metals
metal–metal interactions
peptides
Structural analysis
structure elucidation
Superconducting quantum interference devices
through-bond interaction
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Summary:Developing tunable motifs for heterometallic interactions should be beneficial for fabricating functional materials based on cooperative electronic communications between metal centers. Reported here is the efficient formation of cyclic heterometallic interactions from a complex containing an artificial tripeptide with metal binding sites on its main chain and side chains. X‐ray structural analysis and X‐ray absorption spectroscopy revealed that the cyclic metal–metal arrangements arise from the amide groups connecting four square‐planar CuII centers and four octahedral NiII centers in a cyclic manner. UV/Vis spectral studies suggested that this efficient formation was achieved by the selective formation of the square‐planar CuII centers and a crystallization process. Magnetic measurements using SQUID clarified that the cyclic complex represented the S=2 spin state at low temperatures due to effective antiferromagnetic interactions between the NiII and CuII centers. A cyclic CuII‐NiII arrangement was efficiently formed using a flexible tripeptide and it exhibits effective antiferromagnetic spin coupling through the tripeptide amide groups.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202013373