Enhancement of Magneto-Chiral Dichroism Intensity by Chemical Design: The Key Role of Magnetic-Dipole Allowed Transitions.

Here we report on the strong magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption up to 5.0 T on {Er5Ni6} metal clusters obtained by reaction of enantiopure chiral ligands and NiII and ErIII precursors. Single-crystal diffraction analysis reveals that these compounds are 3d-4f heterometallic clusters, showing helical chirality. MChD spectroscopy reveals a high gMChD dissymmetry factor of ca. 0.24 T-1 (T = 4.0 K, B = 1.0 T) for the 4I13/2 ← 4I15/2 magnetic-dipole allowed electronic transition of the ErIII centers. This record value is 1 or 2 orders of magnitude higher than that of the d-d electronic transitions of the NiII ions and the others f-f electric-dipole induced transitions of the ErIII centers. These findings clearly show the key role that magnetic-dipole allowed transitions have in the rational design of chiral lanthanide systems showing strong MChD.

Magneto-Chiral Dichroism in a One-Dimensional Assembly of Helical Dysprosium(III) Single-Molecule Magnets.

Here we report magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption of a chiral dysprosium(III) coordination polymer. The two enantiomers of [DyIII(H6(py)2)(hfac)3]n [H6(py)2 = 2,15-bis(4-pyridyl)ethynylcarbo[6]helicene; hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate], where the chirality is provided by a functionalized helicene ligand, were structurally, spectroscopically, and magnetically investigated. Magnetic measurements reveal a slow relaxation of the magnetization, with differences between enantiopure and racemic systems rationalized on the basis of theoretical calculations. When the enantiopure complexes are irradiated with unpolarized light in a magnetic field, they exhibit multiple MChD signals associated with the f-f electronic transitions of DyIII, thus providing the coexistence of MChD-active absorptions and single-molecule-magnet (SMM) behavior. These findings clearly show the potential that rationally designed chiral SMMs have in enabling the optical readout of magnetic memory through MChD.

Induced circular dichroism from helicoidal nano substrates to porphyrins: the role of chiral self-assembly.

Because the combination of chiral and magnetic properties is becoming more and more attractive for magneto-chiral phenomena, we here aim at exploring the induction of chirality to achiral magnetic molecules as a strategy for the preparation of magneto-chiral objects. To this end, we have associated free base- and metallo-porphyrins with silica nano helices, using a variety of elaboration methods, and have studied them mainly by electronic natural circular dichroism (NCD) and magnetic circular dichroism (MCD) spectroscopies. While electrostatic or covalent surface grafting uniformly yielded very low induced CD (ICD) for the four assayed porphyrins, a moderate response was observed when the porphyrins were incorporated into the interior of the double-walled helices, likely due to the association of the molecules with the chirally-organized gemini surfactant. A generally stronger, but more variable, ICD was observed when the molecules were drop casted onto the helices immobilised on a quartz plate, likely due to the different capacities of the porphyrins to aggregate into chiral assemblies. Electronic spectroscopy, electron microscopy and IR spectroscopy were used to interpret the patterns of aggregation and their influence on ICD and MCD. No enhancement of MCD was observed as a result of association with the nanohelices except in the case of the free base, 5,10,15,20-tetra-(4-sulfonatophenyl)porphyrin (TPPS). This nanocomposite demonstrated a large ICD in the Soret region and a large MCD in the Q-region due to J-aggregation. However, no induced MChD was observed, possibly due to the spectral mismatch between the ICD and MCD peaks.

Multifunctional Helicene-Based Ytterbium Coordination Polymer Displaying Circularly Polarized Luminescence, Slow Magnetic Relaxation and Room Temperature Magneto-Chiral Dichroism.

The combination of physical properties sensitive to molecular chirality in a single system allows the observation of fascinating phenomena such as magneto-chiral dichroism (MChD) and circularly polarized luminescence (CPL) having potential applications for optical data readout and display technology. Homochiral monodimensional coordination polymers of YbIII were designed from a 2,15-bis-ethynyl-hexahelicenic scaffold decorated with two terminal 4-pyridyl units. Thanks to the coordination of the chiral organic chromophore to Yb(hfac)3 units (hfac- =1,1,1,5,5,5-hexafluoroacetylaconate), efficient NIR-CPL activity is observed. Moreover, the specific crystal field around the YbIII induces a strong magnetic anisotropy which leads to a single-molecule magnet (SMM) behaviour and a remarkable room temperature MChD. The MChD-structural correlation is supported by computational investigations.

Investigation by Chemical Substitution within 2p-3d-4f Clusters of the Cobalt(II) Role in the Magnetic Behavior of [vdCoLn]2 (vd = Verdazyl Radical).

1,5-Dimethyl-3-(3'-(hydroxymethyl)-2'-pyridine)-6-oxotetrazane (H3vdpyCH2OH) or its oxidized verdazyl form (vdpyCH2OH) reacted with transition metal and/or lanthanide acetates to yield [(vdpyCH2O)2Co2Ln2(acO)8] (Ln = Y(III): ICo,Y; Gd(III): ICo,Gd), [(vdpyCH2O)2M3(acO)4] (M = Zn(II): IIZn; Co(II): IICo) and [(vdpyCH2OH)Zn(acO)2] (IIIZn) through self-assembly implying a complex-as-ligand intermediate. Single-crystal diffraction reveals that IMT,Ln are composed of 2p-3d-4f centrosymmetric clusters with verdazyl radicals at the two ends coordinated to the transition-metal ion in a tridentate mode and to the {Ln2(acO)4} lanthanide central core in a monodentate mode through its alkoxo moiety. In ICo,Gd, the transition-metal ions adopt an irregular octahedral environment, and the {Ln2(acO)4} core adopts a paddlewheel motif, whereas in ICo,Y, the transition metal is pentacoordinated, and the central core contains only two acetate bridges. Going from ICo,Y to IICo, the central {Y2(acO)4} core is replaced by an axially compressed octahedral cobalt(II) center, whereas the outer parts of the molecule remain still. The dc magnetic studies revealed that the alternate π-stacking of the verdazyl radicals in IIZn led to the formation of alternate antiferromagnetically coupled 1D chains with Jvd-vd = -8.2(1) cm-1 and Jvd-vd' = -7.6(1) cm-1 (-2J convention). In ICo,Y, a complex fitting procedure allowed us to retrieve a complete set of magnetic parameters to take into account both the magnetic anisotropy of the cobalt(II) centers and intra- and inter-molecular exchange effects. For ICo,Y, it led to gCo = 2.13(4), DCo = 100(2) cm-1, ECo = 19.9(5) cm-1, JCo-vd = +26.5(4) cm-1, and Jvd-vd = -7.95(4) cm-1. ac magnetic susceptibility of ICo,Y, ICo,Gd and IICo did not reveal any slow relaxation of the magnetization even when a dc external magnetic field up to 2000 Oe was applied.

Magnetic 3d-4f Chiral Clusters Showing Multimetal Site Magneto-Chiral Dichroism.

Here, we report the molecular self-assembly of hydroxido-bridged {Ln5Ni6} ((Ln3+ = Dy3+, Y3+) metal clusters by the reaction of enantiopure chiral ligands, namely, (R/S)-(2-hydroxy-3-methoxybenzyl)-serine), with NiII and LnIII precursors. Single-crystal diffraction analysis reveals that these compounds are isostructural sandwich-like 3d-4f heterometallic clusters showing helical chirality. Direct current magnetic measurements on {Dy5Ni6} indicates ferromagnetic coupling between DyIII and NiII centers, whereas those on {Y5Ni6} denote that the NiII centers are antiferromagnetically coupled and/or magnetically anisotropic. Magneto-chiral dichroism (MChD) measurements on {Dy5Ni6} and its comparison to that of {Y5Ni6} provide the first experimental observation of intense multimetal site MChD signals in the visible-near-infrared region. Moreover, the comparison of MChD with natural and magnetic circular dichroism spectra unambiguously demonstrate for the first time that the MChD signals associated with the NiII d-d transitions are mostly driven by natural optical activity and those associated with the DyIII f-f transitions are driven by magnetic optical activity.

Magneto-chiral anisotropy: From fundamentals to perspectives.

The interplay between chirality and magnetic fields gives rise to a cross effect referred to as magneto-chiral anisotropy (MChA), which can manifest itself in different physical properties of chiral magnetized materials. The first experimental demonstration of MChA was by optical means with visible light. Further optical manifestations of MChA have been evidenced across most of the electromagnetic spectrum, from terahertz to X-rays. Moreover, exploiting the versatility of molecular chemistry toward chiral magnetic systems, many efforts have been made to identify the microscopic origins of optical MChA, necessary to advance the effect toward technological applications. In parallel, the replacement of light by electric current has allowed the observation of nonreciprocal electrical charge transport in both molecular and inorganic conductors as a result of electrical MChA (eMChA). MChA in other domains such as sound propagation, photochemistry, and electrochemistry are still in their infancy, with only a few experimental demonstrations, and offer wide perspectives for further studies with potentially large impact, like the understanding of the homochirality of life. After a general introduction to MChA, we give a complete review of all these phenomena, particularly during the last decade.

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

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 (gMChD 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.

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

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 [MnIII(cyclam)(SO4)]ClO4·H2O (cyclam = 1,4,8,11-tetraazacyclotetradecane) featuring antiferromagnetically coupled anisotropic MnIII ions. Alternate current susceptibility measurements revealed the existence of a single-chain magnet behavior hidden below the canted antiferromagnetism (TN = 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 MnIII 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 MnIII ion. These findings set a clear route toward the design and preparation of highly MChD-responsive molecular materials.

Magneto-Chiral Dichroism: A Playground for Molecular Chemists.

Magneto-chiral dichroism (MChD) is a non-reciprocal manifestation of light-matter interaction that can be observed in chiral systems possessing a magnetization, either spontaneous or induced by an external magnetic field. It features a differential absorption 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 absolute configuration of the 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 a fundamental role in technological applications, such as optical readout of magnetic data with unpolarized light. With this Minireview, the authors provide a precise description of this unconventional effect, recall the main results obtained so far and, highlighting new challenges, underline the opportunities opened to molecular chemists interested in investigating this fascinating effect with implications in chemistry and beyond.

A Chiral Prussian Blue Analogue Pushes Magneto-Chiral Dichroism Limits.

Here we report on magneto-chiral dichroism (MChD) detected with visible light on the chiral Prussian Blue Analogue [MnII(X-pnH)(H2O)][CrIII(CN)6]·H2O (X = S, R; pn = 1,2-propanediamine). Single crystals suitable for magneto-optical measurements were grown starting from enantiopure chiral ligands. X-ray diffraction and magnetic measurements confirmed the 2D-layered structure of the material, its absolute configuration, and its ferrimagnetic ordered state below a critical temperature TC of 38 K. Absorption and MChD spectra were measured between 450 and 900 nm from room temperature down to 4 K. At 4 K the electronic spectrum features spin-allowed and spin-forbidden transitions of CrIII centers, spin-forbidden transitions of the MnII centers, and metal-to-metal charge transfer bands. The MChD spectra below the magnetic ordering temperature exhibit intense absolute configuration-dependent MChD signals. The temperature dependence of these signals closely follows the material magnetization. Under a magnetic field of 0.46 T, the most intense contribution to MChD represents 2.6% T-1 of the absorbed intensity, one of the highest values observed to date.

Filling the Gap in Extended Metal Atom Chains: Ferromagnetic Interactions in a Tetrairon(II) String Supported by Oligo-α-pyridylamido Ligands.

The stringlike complex [Fe4(tpda)3Cl2] (2; H2tpda = N2, N6-bis(pyridin-2-yl)pyridine-2,6-diamine) was obtained as the first homometallic extended metal atom chain based on iron(II) and oligo-α-pyridylamido ligands. The synthesis was performed under strictly anaerobic and anhydrous conditions using dimesityliron, [Fe2(Mes)4] (1; HMes = mesitylene), as both an iron source and a deprotonating agent for H2tpda. The four lined-up iron(II) ions in the structure of 2 (Fe···Fe = 2.94-2.99 Å, Fe···Fe···Fe = 171.7-168.8°) are wrapped by three doubly deprotonated twisted ligands, and the chain is capped at its termini by two chloride ions. The spectroscopic and electronic properties of 2 were investigated in dichloromethane by UV-vis-NIR absorption spectroscopy, 1H NMR spectroscopy, and cyclic voltammetry. The electrochemical measurements showed four fully resolved, quasi-reversible one-electron-redox processes, implying that 2 can adopt five oxidation states in a potential window of only 0.8 V. Direct current (dc) magnetic measurements indicate dominant ferromagnetic coupling at room temperature, although the ground state is only weakly magnetic. On the basis of density functional theory and angular overlap model calculations, this magnetic behavior was explained as being due to two pairs of ferromagnetically coupled iron(II) ions ( J = -21 cm-1 using JS i·S j convention) weakly antiferromagnetically coupled with each other. Alternating-current susceptibility data in the presence of a 2 kOe dc field and at frequencies up to 1.5 kHz revealed the onset of slow magnetic relaxation below 2.8 K, with the estimated energy barrier Ueff/ kB = 10.1(1.3) K.

Versatile synthesis of chiral 6-oxoverdazyl radical ligands - new building blocks for multifunctional molecule-based magnets.

A versatile synthetic methodology to access the first family of chiral verdazyl N,N'-chelate ligands is described and exemplified by N,N'-dimethyl-, N,N'-di-isopropyl- and N,N'-diphenyl oxoverdazyls bearing two isomers of the pinene-pyridine functional group. Their physical properties were probed by X-band EPR spectroscopy, cyclic voltammetry and DFT calculations. Preliminary reactivity studies show they can act as N,N'-chelate ligands affording a chiral 1 : 1 complex (3b) with CuCl2, which was characterized by single-crystal X-ray diffraction. Variable temperature EPR studies on (3b) confirm the presence of antiferromagnetic interactions between the spins of the Cu(ii) ion and the verdazyl radical.

From Positive to Negative Zero-Field Splitting in a Series of Strongly Magnetically Anisotropic Mononuclear Metal Complexes.

A series of mononuclear [M(hfa)2(pic)2] (Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; pic = 4-methylpyridine; M = FeII, CoII, NiII, ZnII) compounds were obtained and characterized. The structures of the complexes have been resolved by single-crystal X-ray diffraction, indicating that, apart from the zinc derivative, the complexes are in a trans configuration. Moreover, a dramatic lenghthening of the Fe-N distances was observed, whereas the nickel(II) complex is almost perfectly octahedral. The magnetic anisotropy of these complexes was thoroughly studied by direct-current (dc) magnetic measurements, high-field electron paramagnetic resonance, and infrared (IR) magnetospectroscopy: the iron(II) derivative exhibits an out-of-plane anisotropy (DFe = -7.28 cm-1) with a high rhombicity, whereas the cobalt(II) and nickel(II) complexes show in-plane anisotropy (DCo ∼ 92-95 cm-1; DNi = 4.920 cm-1). Ab initio calculations were performed to rationalize the evolution of the structure and identify the excited states governing the magnetic anisotropy along the series. For the iron(II) complex, an out-of-phase alternating-current (ac) magnetic susceptibility signal was observed using a 0.1 T dc field. For the cobalt(II) derivative, the ac magnetic susceptibility shows the presence of two field-dependent relaxation phenomena: at low field (500 Oe), the relaxation process is beyond single-ion behavior, whereas at high field (2000 Oe), the relaxation of magnetization implies several mechanisms including an Orbach process with Ueff = 25 K and quantum tunneling of magnetization. The observation by µ-SQUID magnetization measurements of hysteresis loops of up to 1 K confirmed the single-ion-magnet behavior of the cobalt(II) derivative.

A novel oxalate-based three-dimensional coordination polymer showing magnetic ordering and high proton conductivity.

A novel three-dimensional (3D) coordination polymer with the formula (C3N2H5)4[MnCr2(ox)6]·5H2O (2), where ox = oxalate and C3N2H5 = imidazolium cation, is reported. Single crystal X-ray diffraction reveals that this porous coordination polymer adopts a chiral three-dimensional quartz-like architecture, with the guest imidazolium cations and water molecules being hosted in its pores. This novel multifunctional material exhibits both a ferromagnetic ordering at TC = 3.0 K, related to the host MnCr2 network, and high proton conductivity [1.86 × 10-3 S cm-1 at 295 K and 88% relative humidity (RH)] due to the presence of the acidic imidazolium cations and free water molecules. The similarity of the structure of compound 2 to that of the previously reported analogous compound (NH4)4[MnCr2(ox)6]·4H2O, (1), also allows us to analyse, to a certain extent, the effect of the acidity of the proton donating guest molecules on proton conduction properties. 2 hosts, in one-dimensional (1D) channels, imidazolium cations, which are more acidic than the ammonium ones in 1 and, as a consequence, 2 shows higher proton conduction than 1, highlighting the effect of the pKa of the proton donating guest molecules on proton conductivity.

Twisting induces ferromagnetism in homometallic clusters.

A helical chiral cluster bridging two sets of Cu2 units is reported. The two double-stranded ligands induce a distorted tetrahedral environment for one of the two copper(ii) ions whereas the second one remains in a standard octahedral environment. Magnetic measurements and wavefunction calculations demonstrate that the copper(ii) centres are ferromagnetically coupled (J = 7.7 cm-1). This ligand-driven ferromagnetic interaction thus appears as a proof-of-concept of an innovative strategy towards high-spin clusters.

Postsynthetic Approach for the Rational Design of Chiral Ferroelectric Metal-Organic Frameworks.

Ferroelectrics (FEs) are materials of paramount importance with a wide diversity of applications. Herein, we propose a postsynthetic methodology for the smart implementation of ferroelectricity in chiral metal-organic frameworks (MOFs): following a single-crystal to single-crystal cation metathesis, the Ca2+ counterions of a preformed chiral MOF of formula Ca6II{CuII24[(S,S)-hismox]12(OH2)3}·212H2O (1), where hismox is a chiral ligand derived from the natural amino acid l-histidine, are replaced by CH3NH3+. The resulting compound, (CH3NH3)12{CuII24[(S,S)-hismox]12(OH2)3}·178H2O (2), retains the polar space group of 1 and is ferroelectric below 260 K. These results open a new synthetic avenue to enlarge the limited number of FE MOFs.

An iron(iii)-centred ferric wheel Fe⊂{Fe6} with a siloxane-based bis-salicylidene Schiff base.

A new iron(iii)-centred ferric wheel Fe⊂{Fe6} of the formula [Fe7(H2L)6(NCS)6](ClO4)3·10H2O, where H4L = N,N'-bis(3-carboxylsalicylidene)-1,3-bis(3-aminopropyl)tetramethyldisiloxane, was synthesised and fully characterised. 57Fe Mössbauer spectra indicate the presence of high spin (S = 5/2) Fe3+ cations adopting a slightly different coordination environment in agreement with the X-ray diffraction structure. There are competing antiferromagnetic exchange interactions along the rim (J1 = -1.00 cm-1) and the radius (J2 = -1.46 cm-1) of the wheel.

Verdazyl Radical, a Building Block for a Six-Spin-Center 2p-3d-4f Single-Molecule Magnet.

The versatile verdazyl family provides a new member as its reduced form 1,5-dimethyl-3-[3'-(hydroxymethyl)-2'-pyridine]-6-oxotetrazane (H3vdpyCH2OH). Upon oxidation and deprotonation in the presence of the acetate salts of CoII and DyIII, the vdpyCH2OH radical is able to self-assemble [(vdpyCH2O)2Co2Dy2ac8] (Hac = HO2CCH3), a 2p-3d-4f cluster displaying single-molecule-magnet properties.

Solvent-Dependent Self-Assembly of an Oxalato-Based Three-Dimensional Magnet Exhibiting a Novel Architecture.

The old but evergreen family of bimetallic oxalates still offers innovative and interesting results. When (Me4N)3[Cr(ox)3]·3H2O is reacted with Mn(II) ions in a nonaqueous solvent, a novel three-dimensional magnet of the formula [N(CH3)4]6[Mn3Cr4(ox)12]·6CH3OH is obtained instead of the one-dimensional compound obtained in water. This new material exhibits an unprecedented stoichiometry with a binodal (3,4) net topology and the highest critical temperature (TC = 7 K) observed so far in a manganese-chromium oxalate based magnet.