Hierarchically Assembled Gigantic Fe/Co Cyanometallate Clusters Exhibiting Electron Transfer Behavior Above Room Temperature.

Autor: Chen ZY; Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China., Xie KP; Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China.; School of Chemistry and Materials Engineering, Huizhou University, Huizhou, 516007, China., Cheng Y; Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China., Deng YF; Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China., Zhang YZ; Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China.
Jazyk: angličtina
Zdroj: Advanced science (Weinheim, Baden-Wurttemberg, Germany) [Adv Sci (Weinh)] 2024 Aug; Vol. 11 (30), pp. e2402884. Date of Electronic Publication: 2024 Jun 14.
DOI: 10.1002/advs.202402884
Abstrakt: The construction of large and complex supramolecular architectures through self-assembly is at the forefront of contemporary coordination chemistry. Notwithstanding great success in various systems using anionic bridges (e.g., O 2- or S 2- ) or organic ligands (e.g., pyridine or carboxylate ligands), the assembly of large cyanide-bridged clusters with increasing nuclearity remains a formidable synthetic challenge. In this study, it is achieved in preparing two heterometallic cyanometallate clusters with unprecedented complexity, [Fe 20 Co 20 ] (1) and [Fe 12 Co 15 ] (2), by creating the "flexibility" through a versatile ligand of bis((1H-imidazol-4-yl)methylene)hydrazine (H 2 L) and low-coordinate cobalt. Complex 1 features a super-square array of four cyanide-bridged [Fe 4 Co 4 ] cube subunits as the corners that are interconnected by four additional [FeCo] units, resulting in a torus-shaped architecture. Complex 2 contains a lantern-like core-shell cluster with a triple-helix kernel of [Co 3 L 3 ] enveloped by a [Fe 12 Co 12 ] shell. The combined structure analysis and mass spectrometry study reveal a hierarchical assembly mechanism, which sheds new light on constructing cyanometallate nanoclusters with atomic precision. Moreover, complex 1 undergoes a thermally induced electron-transfer-coupled spin transition (ETCST) between the diamagnetic {Fe II LS (µ-CN)Co III LS } and paramagnetic {Fe III LS (µ-CN)Co II HS } configurations (LS = low spin, HS = high spin) above room temperature, representing the largest molecule displaying electron transfer and spin transition characteristic.
(© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)
Databáze: MEDLINE
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