White Light Emissive DyIII Single‐Molecule Magnets Sensitized by Diamagnetic [CoIII(CN)6]3− Linkers |
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| Authors: | Dr Szymon Chorazy Dr Micha? Rams Dr Koji Nakabayashi Prof?Dr Barbara Sieklucka Prof?Dr Shin‐ichi Ohkoshi |
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| Affiliation: | 1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, Japan;2. Faculty of Chemistry, Jagiellonian University, Kraków, Poland;3. Institute of Physics, Jagiellonian University, Kraków, Poland |
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| Abstract: | The self‐assembly of DyIII–3‐hydroxypyridine (3‐OHpy) complexes with hexacyanidocobaltate(III) anions in water produces cyanido‐bridged {DyIII(3‐OHpy)2(H2O)4] CoIII(CN)6]}?H2O ( 1 ) chains. They reveal a single‐molecule magnet (SMM) behavior with a large zero direct current (dc) field energy barrier, ΔE=266(12) cm?1 (≈385 K), originating from the single‐ion property of eight‐coordinated DyIII of an elongated dodecahedral geometry, which are embedded with diamagnetic CoIII(CN)6]3? ions into zig‐zag coordination chains. The SMM character is enhanced by the external dc magnetic field, which results in the ΔE of 320(23) cm?1 (≈460 K) at Hdc=1 kOe, and the opening of a butterfly hysteresis loop below 6 K. Complex 1 exhibits white DyIII‐based emission realized by energy transfer from CoIII and 3‐OHpy to DyIII. Low temperature emission spectra were correlated with SMM property giving the estimation of the zero field ΔE. 1 is a unique example of bifunctional magneto‐luminescent material combining white emission and slow magnetic relaxation with a large energy barrier, both controlled by rich structural and electronic interplay between DyIII, 3‐OHpy, and CoIII(CN)6]3?. |
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| Keywords: | cobalt cyanides dysprosium lanthanides luminescence |
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