Near-infrared emissive Er(iii) and Yb(iii) molecular nanomagnets in metal–organic chains functionalized by octacyanidometallates(iv)

Photoluminescent single-molecule magnets are formed in lanthanide(pyrazine N,N′-dioxide) chains with octacyanidometallate(iv) coordination branches playing a crucial role in sensitized NIR emission.

Download Full-text

Near-Infrared Emissive Cyanido-Bridged {YbFe2} Molecular Nanomagnets Sensitive to the Nitrile Solvents of Crystallization

Magnetochemistry ◽

10.3390/magnetochemistry7060079 ◽

2021 ◽

Vol 7 (6) ◽

pp. 79

Author(s):

Michal Liberka ◽

Kseniia Boidachenko ◽

Jakub J. Zakrzewski ◽

Mikolaj Zychowicz ◽

Junhao Wang ◽

...

Keyword(s):

Single Molecule ◽

Self Assembly ◽

Near Infrared ◽

Magnetic Data ◽

Phonon Modes ◽

Single Molecule Magnets ◽

Molecular Nanomagnets ◽

Dipole Interactions ◽

Raman Process ◽

Slow Magnetic Relaxation

One of the pathways toward luminescent single-molecule magnets (SMMs) is realized by the self-assembly of lanthanide(3+) ions with cyanido transition metal complexes. We report a novel family of emissive SMMs, {YbIII(4-pyridone)4[FeII(phen)2(CN)2]2}(CF3SO3)3·solv (solv = 2MeCN, 1·MeCN; 2AcrCN, 1·AcrCN; 2PrCN, 1·PrCN; 2MalCN·1MeOH; 1·MalCN; MeCN = acetonitrile, AcrCN = acrylonitrile, PrCN = propionitrile, MalCN = malononitrile). They are based on paramagnetic YbIII centers coordinating diamagnetic [FeII(phen)2(CN)2] metalloligands but differ in the nitrile solvents of crystallization. They exhibit a field-induced slow magnetic relaxation dominated by a Raman process, without an Orbach relaxation as indicated by AC magnetic data and the ab initio calculations. The Raman relaxation is solvent-dependent as represented by the power “n” of the BRamanTn contribution varying from 3.07(1), to 2.61(1), 2.37(1), and 1.68(4) for 1·MeCN, 1·PrCN, 1·AcrCN, and 1·MalCN, respectively, while the BRaman parameter adopts the opposite trend. This was correlated with the variation of phonon modes schemes, including the number of available vibrational modes and their energies, dependent on the increasing complexity of the applied nitrile. 1·MeCN and 1·MalCN show the additional T-independent relaxation assignable to dipole-dipole interactions as confirmed by its suppression in 1·AcrCN and 1·PrCN revealing longer Yb–Yb distances and the disappearance in the LuIII-diluted 1·MeCN@Lu. All compounds exhibit YbIII–centered near-infrared photoluminescence sensitized by organic ligands.

Download Full-text

Metal-Organic Frameworks: Derived from Single Molecule Magnets

Encyclopedia of Inorganic and Bioinorganic Chemistry ◽

10.1002/9781119951438.eibc2220 ◽

2014 ◽

pp. 1-14 ◽

Cited By ~ 1

Author(s):

Athanassios D. Katsenis ◽

Euan K. Brechin ◽

Giannis S. Papaefstathiou

Keyword(s):

Single Molecule ◽

Metal Organic Frameworks ◽

Single Molecule Magnets ◽

Metal Organic

Download Full-text

Metal–Organic Frameworks as Playgrounds for Reticulate Single-Molecule Magnets

Inorganic Chemistry ◽

10.1021/acs.inorgchem.9b02086 ◽

2019 ◽

Vol 58 (21) ◽

pp. 14498-14506 ◽

Cited By ~ 6

Author(s):

Lucas H. G. Kalinke ◽

Danielle Cangussu ◽

Marta Mon ◽

Rosaria Bruno ◽

Estefania Tiburcio ◽

...

Keyword(s):

Single Molecule ◽

Metal Organic Frameworks ◽

Single Molecule Magnets ◽

Metal Organic

Download Full-text

Molecular nanomagnets

10.1093/oxfordhb/9780199533060.013.4 ◽

2017 ◽

Author(s):

W. Wernsdorfer

Keyword(s):

Molecular Electronics ◽

Single Molecule ◽

Quantum Dynamics ◽

Spin Model ◽

Photon Absorption ◽

Single Molecule Magnets ◽

Molecular Nanomagnets ◽

Quantum Properties ◽

Molecular Spintronics ◽

Quantum Phenomena

This article describes the quantum phenomena observed in molecular nanomagnets. Molecular nanomagnets, or single-molecule magnets (SMMs), provides a fundamental link between spintronics and molecular electronics. SMMs combine the classic macroscale properties of a magnet with the quantum properties of a nanoscale entity. The resulting field, molecular spintronics, aims at manipulating spins and charges in electronic devices containing one or more molecules. This article first considers molecular nanomagnets and the giant spin model for nanomagnets before discussing the quantum dynamics of a dimer of nanomagnets, resonant photon absorption in Cr7Ni antiferromagnetic rings, and photon-assisted tunnelling in a single-molecule magnet. It also examines environmental decoherence effects in nanomagnets and concludes by highlighting the new trends towards molecular spintronics using junctions and nano-SQUIDs.

Download Full-text

Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

Magnetochemistry ◽

10.3390/magnetochemistry4040044 ◽

2018 ◽

Vol 4 (4) ◽

pp. 44 ◽

Cited By ~ 4

Author(s):

Gang Huang ◽

Guillaume Calvez ◽

Yan Suffren ◽

Carole Daiguebonne ◽

Stéphane Freslon ◽

...

Keyword(s):

Single Molecule ◽

Near Infrared ◽

Color Change ◽

Infrared Emission ◽

Single Molecule Magnet ◽

Light Lanthanide ◽

Nir Emission ◽

Dimeric Compound ◽

Near Infrared Emission ◽

Derivatives Of

Up to now, even if murexide-based complexometric studies are performed with all 3d or 4f ions, the crystal structures of the light-lanthanide derivatives of the lanthanide-murexide series are unknown. In this work, we report the crystal structure of the NdIII derivative named NdMurex. Contrary to all known complexes of the 3d or 4f series, a dimeric compound was obtained. As for its already reported DyIII and YbIII parents, the NdIII complex responsible for the color-change behaves as a single-molecule magnet (SMM). This behavior was observed on both the crystalline (NdMurex: Ueff = 6.20(0.80) K, 4.31 cm−1; τ0 = 2.20(0.92) × 10−5 s, Hdc = 1200 Oe) and anhydrous form (NdMurexAnhy: Ueff = 6.25(0.90) K, 4.34 cm−1; τ0 = 4.85(0.40) × 10−5 s, Hdc = 1200 Oe). The SMM behavior is reported also for the anhydrous CeIII derivative (CeMurexAnhy: Ueff = 5.40(0.75) K, 3.75 cm−1; τ0 = 3.02(1.10) × 10−5 s, Hdc = 400 Oe). The Near-Infrared Emission NIR emission was observed for NdMurexAnhy and highlights its bifunctionality.

Download Full-text