Photoluminescent Lanthanide(III) Single‐Molecule Magnets in Three‐Dimensional Polycyanidocuprate(I)‐Based Frameworks

• Published in: Chemistry : a European journal Vol. 25; no. 51; pp. 11820 - 11825
• Main Authors: Zakrzewski, Jakub J., Chorazy, Szymon, Nakabayashi, Koji, Ohkoshi, Shin‐ichi, Sieklucka, Barbara
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 12.09.2019
• Subjects: Bimetals; Chemistry; Coordination; copper; cyanides; Hysteresis loops; lanthanides; Magnets; Photoluminescence; Photons; Physical properties; single-molecule magnets; copper; photoluminescence; single-molecule magnets; cyanides; lanthanides
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201902420

Three‐dimensional bimetallic cyanido‐bridged frameworks, [LnIII(2,2′‐bipyridine N,N′‐dioxide)2(H2O)][CuI2(CN)5]⋅5 H2O (Ln=Dy, 1; Yb, 2), are reported. They exhibit the effect of slow relaxation of magnetization, leading to a magnetic hysteresis loop, and sensitized visible‐to‐near‐infrared photoluminescence. Both physical properties are related to the eight‐coordinated lanthanide(III) complexes embedded in the unprecedented coordination skeleton composed of symmetry‐breaking polycyanidocuprate linkers. The three‐dimensional d–f cyanido‐bridged network was shown to serve as an efficient coordination scaffold to achieve emissive lanthanide single‐molecule magnets. Quantum magnets in 3D frameworks: Unprecedented three‐dimensional cyanido‐bridged networks based on lanthanide(III) and copper(I) centers were synthesized. They exhibit tunable visible‐to‐NIR photoluminescence and slow relaxation of magnetization effect related to the incorporated 4f metal complexes. The 3D network serves as an efficient coordination scaffold to achieve luminescent single‐molecule magnets.