Spin and charge transfer through hydrogen bonding in [Co(NH3)5(OH2)][Cr(CN)6]

Figgis, Brian N.; Kucharski, E. S.; Vrtis, M.L.

doi:10.1021/ja00054a024

Cited by 64 publications

(37 citation statements)

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“…Theoretical calculations beyond the SCF approximation on [Cu(pba0H}]2-predict negative spin densities around the carbon atoms of the oxamato groups. Such negative spin densities were found through polarized neutron diffraction in the trivalent hexacyanometallates [M(CN)6]3- [13][14][15].…”

Section: -mentioning

confidence: 99%

Bimetallic Molecular-Based Magnetic Materials

Kahn

1996

Molecular Magnetism: From Molecular Assemblies to the Devices

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Among all the molecules and molecular assemblies relevant to molecular magnetism [1], those containing two (or possibly more) kinds of metal ions have played a particularly important role. Two reasons, at least, justify this situation. First, the diversity of the situations which can be encountered concerning the interaction between two spin carriers A and B within a molecular unit is much greater when A and B are different. For instance, the strict orthogonality of the magnetic orbitals leading to the stabilization of the molecular state of highest spin multiplicity is much easier to achieve in heterobimetallic than in homobimetallic species [2]. Secondly, with several kinds of magnetic centers, it is possible to design molecular lattices showing quite peculiar spin topologies. It is in particular the case of ferrimagnetic lattices.The first review article devoted to the magnetism of heteropolymetallic systems appeared in 1987 [3]. Since, this field has developed tremendously, in particular in relation with the synthesis of molecular-based magnets. This short review will be organized around the central theme of bimetallic magnets. The next section reviews some key concepts in molecular magnetism, such as spin delocalization and polarization, and then treats of the interaction between two spin carriers. Each subsequent section, from III to VII, is devoted to one type of bridge which have already allowed to design molecular-based magnets. To date, these bridges are : oxamato, oxamido, oxalato, dithiooxalato, oximato,

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Section: -mentioning

confidence: 99%

Bimetallic Molecular-Based Magnetic Materials

Kahn

1996

Molecular Magnetism: From Molecular Assemblies to the Devices

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“…[9][10][11][12][13] Af ew years ago, we undertook af undamental study of the [Fe III (Tp)(CN) 3 ] À building block with the aim of gaining a deeper understanding of its properties by probing the magnetism at the local level. [19][20][21] To gain information on the ligand spindensity distribution, experimentald iffractiona nalysist echniques can be also combined with quantum chemistry. The rationalization of these macroscopic magnetic properties is then commonlya ddressed by phenomenological approaches based on spin Hamiltonian models.…”

Section: Introductionmentioning

confidence: 99%

Probing the Local Magnetic Structure of the [Fe^III(Tp)(CN)₃]⁻ Building Block Via Solid‐State NMR Spectroscopy, Polarized Neutron Diffraction, and First‐Principle Calculations

Flambard

Garnier

et al. 2019

Chemistry A European J

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The local magnetic structure in the [Fe III (Tp)(CN) 3 ] À building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutrond iffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanidol igands: Spin-polarization on the carbon atomsa nd spin-delocalization on the nitrogen atoms.T he resultso fo ur combined density functional theory (DFT) and multireference calculations were found in good agreementw ith the PND results and the experimen-tal NMR chemical shifts. Moreover,t he ab-initio calculations allowedu st oc onnectt he experimental spin-density map characterized by PNDa nd the suggested distribution of the spin-density on the ligandso bserved by NMR spectroscopy. Interestingly,s ignificant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using as imple point-dipole model. These discrepancies underline the limitation of the pointdipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contacta nd pseudo-contact contributions.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.org/10.1002/chem.201902239.A dditional data regarding the experimental and computational details,experimental NMR data for the diamagnetic reference and the paramagnetic complex, crystal structure data for the diamagnetic reference and the magnetization characterization:DFT spin-densities, NLMOs, g-factors, and HyFCCs for [Fe III (Tp)(CN) 3 ] À .Additional calculated NMR shielding constants and chemical shifts.

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“…Moreover, transmission of magnetic interactions through hydrogen bonds has been demonstrated to be quite efficient in metal complexes [21] and in several hydrogenbonded organic magnets. [17] Despite the interest of having switchable magnetic materials, hydrogen-bonded supramolecular magnetic materials, whose properties may be systematically tuned and/or controlled by external stimuli, are limited to one example.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Photomagnetic Materials: Photoinduced Dimerization of Ferrocene‐Based Polychlorotriphenylmethyl Radicals

Ratera

Ruiz‐Molina

Vidal-Gancedo

et al. 2004

Chemistry A European J

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New ferrocenyl Schiff-base polychlorotriphenylmethyl radicals have been synthesized and characterized. The imino group of one such radical undergoes an irreversible trans to cis structural isomerization induced by light. Such photoinduced isomerization has been monitored by UV/Vis and ESR spectroscopy and also monitored by HPLC. ESR frozen solution experiments at low temperature revealed that the cis isomer dimerizes, showing a strong antiferromagnetic interaction. Although numerous photochromic supramolecular systems have been described, such a photoinduced self-assembly process represents the first example of a one-way photoswitchable magnetic system in which a conversion between a doublet and a singlet ground state species is promoted by a photoinduced dimerization process driven by the formation of hydrogen bonds. DFT calculations on the minimized structure and on the rotational barriers have been performed to establish the origin of such behavior. The effect of the substituents and the media polarity on the photoisomerization of this imine chromophore have also been studied. It has been observed that the efficiency of the process is markedly dependent on the presence and characteristics of electron-donor and electron-acceptor substituents of the ferrocenyl Schiff-base polychlorotriphenylmethyl radicals as well as on the polarity of the solvent.

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Spin and charge transfer through hydrogen bonding in [Co(NH3)5(OH2)][Cr(CN)6]

Cited by 64 publications

References 0 publications

Bimetallic Molecular-Based Magnetic Materials

Bimetallic Molecular-Based Magnetic Materials

Probing the Local Magnetic Structure of the [Fe^III(Tp)(CN)₃]⁻ Building Block Via Solid‐State NMR Spectroscopy, Polarized Neutron Diffraction, and First‐Principle Calculations

Supramolecular Photomagnetic Materials: Photoinduced Dimerization of Ferrocene‐Based Polychlorotriphenylmethyl Radicals

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Spin and charge transfer through hydrogen bonding in [Co(NH3)5(OH2)][Cr(CN)6]

Cited by 64 publications

References 0 publications

Bimetallic Molecular-Based Magnetic Materials

Bimetallic Molecular-Based Magnetic Materials

Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]− Building Block Via Solid‐State NMR Spectroscopy, Polarized Neutron Diffraction, and First‐Principle Calculations

Supramolecular Photomagnetic Materials: Photoinduced Dimerization of Ferrocene‐Based Polychlorotriphenylmethyl Radicals

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Probing the Local Magnetic Structure of the [Fe^III(Tp)(CN)₃]⁻ Building Block Via Solid‐State NMR Spectroscopy, Polarized Neutron Diffraction, and First‐Principle Calculations