Heterotrimetallic {LnOVPt} complexes with antiferromagnetic Ln–V coupling and magnetic memory

Beach, Stephanie A.; Guillet, Jesse L.; Lagueux, Sydney P.; Perfetti, Mauro; Livesay, Brooke N.; Shores, Matthew P.; Bacon, Jeffrey W.; Rheingold, Arnold L.; Arnold, Polly L.; Doerrer, Linda H.

doi:10.1039/d0cc04334f

Cited by 7 publications

(22 citation statements)

References 27 publications

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“…Compared to organic molecular wires, molecules containing transition metal centers have the potential for enhanced conductance , and increased functionality via redox or magnetic properties which can be leveraged to create components such as molecular switches − and memory storage devices. , Metal-centered electronic states or nuclear spin states of molecules containing one or more transition metals can be synthetically tuned and manipulated in situ − for potential applications in spintronics and quantum information science (QIS). − Synthetic efforts to form molecular metal wires include coordination polymers, extended metal atom chains (EMACs), and infinite one-dimensional (1D) chains. − …”

Section: Introductionmentioning

confidence: 99%

Hard–Soft Chemistry Design Principles for Predictive Assembly of Single Molecule-Metal Junctions

et al. 2021

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The achievement of atomic control over the organic–inorganic interface is key to engineering electronic and spintronic properties of molecular devices. We leverage insights from inorganic chemistry to create hard–soft acid–base (HSAB) theory-derived design principles for incorporation of single molecules onto metal electrodes. A single molecule circuit is assembled via a bond between an organic backbone and an under-coordinated metal atom of the electrode surface, typically Au. Here, we study molecular composition factors affecting the junction assembly of coordination complexes containing transition metals atoms on Au electrodes. We employ hetero- and homobimetallic lantern complexes and systematically change the coordination environment to vary the character of the intramolecular bonds relative to the electrode-molecule interaction. We observe that trends in the robustness and chemical selectivity of single molecule junctions formed with a range of linkers correlate with HSAB principles, which have traditionally been used to guide atomic arrangements in the synthesis of coordination complexes. We find that this similarity between the intermolecular electrode-molecule bonding in a molecular circuit and the intramolecular bonds within a coordination complex has implications for the design of metal-containing complexes compatible with electrical measurements on metal electrodes. Our results here show that HSAB principles determine which intramolecular interactions can be compromised by inter molecule-electrode coordination; in particular on Au electrodes, soft–soft metal–ligand bonding is vulnerable to competition from soft–soft Au-linker bonding in the junction. Neutral donor–acceptor intramolecular bonds can be tuned by the Lewis acidity of the transition metal ion, suggesting future synthetic routes toward incorporation of transition metal atoms into molecular junctions for increased functionality of single molecule devices.

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Section: Introductionmentioning

confidence: 99%

Hard–Soft Chemistry Design Principles for Predictive Assembly of Single Molecule-Metal Junctions

et al. 2021

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“…Heterometallic complexes have been studied in many research fields such as luminescence, [1][2][3] catalysis, [4][5][6] and magnetism. [7][8][9][10][11][12][13][14] Luminescence has received particular interest because of its utilization in luminescence devices, bioimaging systems, and photosensitizers. Hasegawa et al…”

Section: Introductionmentioning

confidence: 99%

“…Considerable efforts have thus been devoted to the formation of various intermetallic interactions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] Although highresolution X-ray diffraction analysis can provide insight into the electron density of bonds, 19 theoretical calculations are widely conducted for examining intermetallic interactions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] In this study, we synthesized heterometallic Ln-Pt complexes:…”

Section: Introductionmentioning

confidence: 99%

Hidden Heterometallic Interaction Emerges from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

Yoshida

Shabana

Izuogu

et al. 2022

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Theoretical calculations are typically utilized for examining intermetallic interactions. However, to validate theory, experimental confirmation of the existence of these interactions is necessary. We synthesized new heterometallic Ln–Pt complexes, NEt4{[Pt(PhSAc)4]Ln[(PhSAc)4Pt]}·2DMF (Ln: lanthanoid = Gd (1), Tb (2), Dy (3), PhSAc = benzothioacetate, NEt4 = tetraethylammonium), in which both diamagnetic Pt(II) ions interact with the central Ln(III) ion. Typically, these interactions are not detected, because the distance between Ln and Pt atoms (~3.6 Å) is much larger than the covalent radius (~3.3 Å) and ionic radius (~3.10 Å). Pt-LIII resonant inelastic X-ray scattering (RIXS) analysis was conducted to experimentally confirm the unique influence of the hidden Ln–Pt interaction on the luminescence of the Tb–Pt molecule, where the interaction induced emission properties in the Tb and Pt ions, with high quantum yield (59%). Quantum theory of atoms in molecules (QTAIM) analysis was also used to confirm the experimental results. RIXS analysis allowed the identification of several distinctive characteristics of the coordination environment, including the existence of heterometallic interactions, that affected the observed luminescence.

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“…Heterometallic complexes have been studied in many research fields such as luminescence, − catalysis, − and magnetism. − Luminescence has received particular interest because of its utilization in luminescence devices, bioimaging systems, and photosensitizers. Hasegawa et al reported the thermocontrol emission of a heterometallic Tb(III)–Eu(III) polymer, wherein the energy transfer from the Tb to Eu ion is governed by the thermosensitivity dependence on linker ligands.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, heterometallic interactions also exert an important influence on the physical properties of heterometallic complexes. Considerable efforts have thus been devoted to the formation of various intermetallic interactions. − Although high-resolution X-ray diffraction analysis can provide insight into the electron density of bonds, theoretical calculations are widely conducted for examining intermetallic interactions. − …”

Section: Introductionmentioning

confidence: 99%

Hidden Heterometallic Interaction Emerging from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

et al. 2022

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Theoretical calculations are typically utilized for examining intermetallic interactions. However, to validate the theory, experimental confirmation of the existence of these interactions is necessary. We synthesized new heterometallic Ln−Pt complexes, NEt 4 {[Pt(PhSAc) 4 ]Ln[(PhSAc) 4 Pt]}• 2DMF (Ln: lanthanoid = Gd (1), Tb (2), Dy (3), PhSAc = benzothioacetate, NEt 4 = tetraethylammonium), in which both diamagnetic Pt(II) ions interact with the central Ln(III) ion. Typically, these interactions are not detected because the distance between Ln and Pt atoms (∼3.6 Å) is much larger than the covalent radius (∼3.3 Å) and ionic radius (∼3.10 Å). Pt−L III resonant inelastic X-ray scattering (RIXS) analysis was conducted to experimentally confirm the unique influence of the hidden Ln−Pt interaction on the luminescence of the Tb−Pt molecule, where the interaction induced emission properties in the Tb and Pt ions, with high quantum yield (59%). Quantum theory of atoms in molecules (QTAIM) analysis was also used to confirm the experimental results. RIXS analysis allowed the identification of several distinctive characteristics of the coordination environment, including the existence of heterometallic interactions, that affected the observed luminescence.

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Heterotrimetallic {LnOVPt} complexes with antiferromagnetic Ln–V coupling and magnetic memory

Abstract: PtVO(SOCR)4 lantern complexes and Ce(OAr)3 or Nd(OAr)3 form heterotrimetallic [Ln(OAr)3{PtVO(SOCR)4}] with linear Ln–OVPt linkages; all four exhibit slow magnetic relaxation and likely antiferromagnetic coupling.

Cited by 7 publications

References 27 publications

Hard–Soft Chemistry Design Principles for Predictive Assembly of Single Molecule-Metal Junctions

Hard–Soft Chemistry Design Principles for Predictive Assembly of Single Molecule-Metal Junctions

Hidden Heterometallic Interaction Emerges from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

Hidden Heterometallic Interaction Emerging from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

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