Local-Site Dependency of Magneto-Chiral Dichroism in Enantiopure One-Dimensional Copper(II)–Chromium(III) Coordination Polymers

Taniguchi, Kouji; Kishiue, Shuhei; Kimura, Shojiro; Miyasaka, Hitoshi

doi:10.7566/jpsj.88.093708

Cited by 14 publications

(19 citation statements)

References 16 publications

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“…A similar observation has been made by Taniguchi and co‐workers through the investigation of the MChD response of a chiral heterometallic system formulated as [Cu II ((1X,2X)‐chxn) 2 ] 3 [Cr III (CN) 6 ] 2 ⋅ n H 2 O (X= S,S ; R,R ; chxn=1,2‐diamino‐cyclohexane) . A weak MChD signal was observed for the electronic d–d transition of the Cu II ion coordinated to the chiral chxn ligand, while the [Cr III (CN) 6 ] 3− moiety do not provide any detectable MChD response .…”

Section: Mchd In Molecular Magnetsmentioning

confidence: 99%

Magneto‐Chiral Dichroism: A Playground for Molecular Chemists

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2020

Chemistry A European J

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Magneto-chiral dichroism (MChD)i sanon-reciprocal manifestation of light-matteri nteraction that can be observed in chiral systems possessing am agnetization, either spontaneousorinduced by an externalmagnetic field.Itfeatures ad ifferentiala bsorption or emission of unpolarized light that depends on the relative orientation of the magnetization with respect to the direction of the light propagation vector and on the absolutec onfigurationo ft he system. Molecular chemistry is the best-suited route towards systems combining chirality and magnetism. Nowadays, investigation of MChD is still in its infancy although this effect might play af undamentalr olei nt echnological applications, such as optical readouto fm agnetic dataw ith unpolarized light. With this Minireview,t he authors provideaprecise description of this unconventional effect, recall the main results obtained so far and, highlighting new challenges, underline the opportunities openedt om olecular chemists interested in investigating this fascinating effect with implications in chemistry and beyond.

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Section: Mchd In Molecular Magnetsmentioning

confidence: 99%

Magneto‐Chiral Dichroism: A Playground for Molecular Chemists

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2020

Chemistry A European J

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“…3,9 Since then, MChD has been observed in specific systems for frequencies ranging from microwaves 10 to hard X-rays, 11,12 underlining the universality of this effect. 13−15 Nonetheless, apparently contradicting results appeared about the microscopic origins of this effect: the studies with X-ray light indicate that the existence of an orbital contribution to the magnetic moment of the absorber is a crucial feature to observe MChD, 11 whereas with visible light MChD is also observed for metal ions with weak orbital moments, such as copper(II), 16 chromium(III), 17,18 or manganese(II). 19 It is thus of utmost importance to unravel the origins of MChD for the electronic transitions falling in the visible range of the electromagnetic spectrum.…”

Section: ■ Introductionmentioning

confidence: 99%

Magnetic Anisotropy Drives Magnetochiral Dichroism in a Chiral Molecular Helix Probed with Visible Light

et al. 2020

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Magnetochiral dichroism (MChD) is a nonreciprocal manifestation of light−matter interaction that can be observed in chiral magnetized systems. It features a differential absorption of unpolarized light depending on the relative orientation of the magnetic field and the light wavevector and on the absolute configuration of the system. The relevance of this effect for optical readout of magnetic data calls for a complete understanding of the microscopic parameters driving MChD with an easy-accessible and nondamaging light source, such as visible light. For this purpose, here we report on MChD detected with visible light on a chiral magnetic helix formulated as [Mn III (cyclam)(SO 4 )]ClO 4 •H 2 O (cyclam = 1,4,8,11-tetraazacyclotetradecane) featuring antiferromagnetically coupled anisotropic Mn III ions. Alternate current susceptibility measurements revealed the existence of a single-chain magnet behavior hidden below the canted antiferromagnetism (T N = 5.8 K) already evidenced by direct current magnetometry. A detailed analysis of the optical absorption gives access to the value of the zero-field splitting parameter D (2.9 cm −1 ), which quantifies the magnetic anisotropy of the Mn III centers. Below the magnetic ordering temperature of the material, the MChD spectra exhibit intense absolute configuration dependent MChD signals reaching record values of ca. 12% of the absorbed intensity for the two electronic transitions most influenced by the spin−orbit coupling of the Mn III ion. These findings set a clear route toward the design and preparation of highly MChD-responsive molecular materials.

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“…A more versatile approach consists of introducing the chirality on the coordinating ligand. Recent studies on transition metal complexes have demonstrated that second coordination sphere chiral features enable MChD without the need for a strongly chiral environment surrounding the metal. − , This opens the door toward the design of a much larger variety of chiral complexes showing MChD. In parallel, the incorporation of inherently chiral ligands into organometallic architectures has shown unique properties resulting from the strong chiroptical response of the ligand and the intrinsic properties of the metal …”

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Helicene-Based Ligands Enable Strong Magneto-Chiral Dichroism in a Chiral Ytterbium Complex

et al. 2021

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Here we report the first experimental observation of magneto-chiral dichroism (MChD) detected through light absorption in an enantiopure lanthanide complex. The P and M enantiomers of [YbIII((X)-L)(hfac)3] (X = P, M; L = 3-(2-pyridyl)-4-aza[6]-helicene; hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate), where the chirality is held by the helicene-based ligand, were studied in the near-infrared spectral window. When irradiated with unpolarized light in a magnetic field, these chiral complexes exhibit a strong MChD signal (g MChD ca. 0.12 T–1) associated with the 2F5/2 ← 2F7/2 electronic transition of YbIII. The low temperature absorption and MChD spectra reveal a fine structure associated with crystal field splitting and vibronic coupling. The temperature dependence of the main dichroic signal detected up to 150 K allowed, for the first time, the disentanglement of the two main microscopic contributions to the dichroic signal predicted by the MChD theory. These findings pave the way toward probing MChD in chiral lanthanide-based single-molecule magnets.

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Local-Site Dependency of Magneto-Chiral Dichroism in Enantiopure One-Dimensional Copper(II)–Chromium(III) Coordination Polymers

Cited by 14 publications

References 16 publications

Magneto‐Chiral Dichroism: A Playground for Molecular Chemists

Magneto‐Chiral Dichroism: A Playground for Molecular Chemists

Magnetic Anisotropy Drives Magnetochiral Dichroism in a Chiral Molecular Helix Probed with Visible Light

Helicene-Based Ligands Enable Strong Magneto-Chiral Dichroism in a Chiral Ytterbium Complex

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