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Hexakis-adducts of [60]fullerene as molecular scaffolds of polynuclear spin-crossover molecules.

ABSTRACT: A family of hexakis-substituted [60]fullerene adducts endowed with the well-known tridentate 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligand for spin-crossover (SCO) systems has been designed and synthesized. It has been experimentally and theoretically demonstrated that these molecular scaffolds are able to form polynuclear SCO complexes in solution. UV-vis and fluorescence spectroscopy studies have allowed monitoring of the formation of up to six Fe(ii)-bpp SCO complexes. In addition, DFT calculations have been performed to model the different complexation environments and simulate their electronic properties. The complexes retain SCO properties in the solid state exhibiting both thermal- and photoinduced spin transitions, as confirmed by temperature-dependent magnetic susceptibility and Raman spectroscopy measurements. The synthesis of these complexes demonstrates that [60]fullerene hexakis-adducts are excellent and versatile platforms to develop polynuclear SCO systems in which a fullerene core is surrounded by a SCO molecular shell.

SUBMITTER: Palacios-Corella M

PROVIDER: S-EPMC8178998 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Playing with the weakest supramolecular interactions in a 3D crystalline hexakis[60]fullerene induces control over hydrogenation selectivity.

Project description:Weak forces can play an essential role in chemical reactions. Controlling such subtle forces in reorganization processes by applying thermal or chemical stimuli represents a novel synthetic strategy and one of the main targets in supramolecular chemistry. Actually, to separate the different supramolecular contributions to the stability of the 3D assemblies is still a major challenge. Therefore, a clear differentiation of these contributions would help in understanding the intrinsic nature as well as the chemical reactivity of supramolecular ensembles. In the present work, a controlled reorganization of an hexakis[60]fullerene-based molecular compound purely governed by the weakest van der Waals interactions known, i.e. the dihydrogen interaction - usually called sticky fingers - is illustrated. This pre-reorganization of the hexakis[60]fullerene under mild conditions allows a further selective hydrogenation of the crystalline material via hydrazine vapors exposure. This unique two-step transformation process is monitored by single-crystal to single-crystal diffraction (SCSC) which allows the direct observation of the molecular movements in the lattice and the subsequent solid-gas hydrogenation reaction.

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Ferroelectric metallomesogens composed of achiral spin crossover molecules.

Project description:Ferroelectric liquid crystals (FLCs) are fascinating functional materials that have a remnant and electrically invertible polarization. To date, typical FLCs have been mainly realized by molecular design such as the incorporation of chirality into a given molecular structure. Here, we report for the first time ferroelectricity induced by spin transition associated with a crystal - liquid crystal phase transition in achiral molecules. Iron(ii) metallomesogens incorporating alkyl chains of type [Fe(3C n -bzimpy)2](BF4)2 (n = 8 (1), 10 (2), 12 (3), 14 (4), 16 (5) and 18 (6); bzimpy = 2,6-bis(benzimidazol-2'-yl)pyridine) that exhibit spin crossover (SCO) phenomena have been synthesized. Compounds 5 and 6 were each demonstrated to show SCO behaviour along with the occurrence of a phase transition between the crystalline (Cr) state and corresponding chiral smectic C (SmC*) state. The distortion of the coordination sphere in the high spin state is seen to trigger the generation of the SmC* state. The liquid crystalline compounds do not display ferroelectric behaviour in their Cr state but do exhibit ferroelectric hysteresis loops in their SmC* state. Ferroelectric switching was clearly confirmed by second harmonic generation (SHG) experiments involving the respective phases. These findings will undoubtedly lead to new strategies for the design of new FLCs based on metal-centred spin transitions.

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Enhanced Thermoelectricity in Metal-[60]Fullerene-Graphene Molecular Junctions.

Project description:The thermoelectric properties of molecular junctions consisting of a metal Pt electrode contacting [60]fullerene derivatives covalently bound to a graphene electrode have been studied by using a conducting-probe atomic force microscope (c-AFM). The [60]fullerene derivatives are covalently linked to the graphene via two meta-connected phenyl rings, two para-connected phenyl rings, or a single phenyl ring. We find that the magnitude of the Seebeck coefficient is up to nine times larger than that of Au-C60-Pt molecular junctions. Moreover, the sign of the thermopower can be either positive or negative depending on the details of the binding geometry and on the local value of the Fermi energy. Our results demonstrate the potential of using graphene electrodes for controlling and enhancing the thermoelectric properties of molecular junctions and confirm the outstanding performance of [60]fullerene derivatives.

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Multivalent Tryptophan- and Tyrosine-Containing [60]Fullerene Hexa-Adducts as Dual HIV and Enterovirus A71 Entry Inhibitors.

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Sequential Tether-Directed Synthesis of New [3 : 2 : 1] Hexakis-Adducts of C<sub>60</sub> with a Mixed Octahedral Addition Pattern.

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| S-EPMC8251792 | biostudies-literature

Spin-state-dependent electrical conductivity in single-walled carbon nanotubes encapsulating spin-crossover molecules.

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Sublimable Spin-Crossover Complexes: From Spin-State Switching to Molecular Devices.

Project description:Spin-crossover (SCO) active transition metal complexes are an important class of switchable molecular materials due to their bistable spin-state switching characteristics at or around room temperature. Vacuum-sublimable SCO complexes are a subclass of SCO complexes suitable for fabricating ultraclean spin-switchable films desirable for applications, especially in molecular electronics/spintronics. Consequently, on-surface SCO of thin-films of sublimable SCO complexes have been studied employing spectroscopy and microscopy techniques, and results of fundamental and technological importance have been obtained. This Review provides complete coverage of advances made in the field of vacuum-sublimable SCO complexes: progress made in the design and synthesis of sublimable functional SCO complexes, on-surface SCO of molecular and multilayer thick films, and various molecular and thin-film device architectures based on the sublimable SCO complexes.

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Molecular solubilization of fullerene C(60) in water by γ-cyclodextrin thioethers.

Project description:Various hydrophilic γ-cyclodextrin (CD) thioethers, containing neutral or ionic side arms were found to form molecular disperse solutions of C(60) in water reaching concentrations of 15 mg/L. Equilibrium state was approached after seven days without the use of organic cosolvents. The 1:2 stoichiometry of the C(60)/γ-CD thioether complexes was demonstrated by a parabolic phase-solubility diagram. In contrast, native γ-CD forms nanoparticles with C(60). Particle sizes of C(60) were determined by dynamic light scattering.

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Photodynamic Activity of Liposomal Photosensitizers via Energy Transfer from Antenna Molecules to [60]Fullerene.

Project description:Photodynamic therapy (PDT) is an emerging approach for the treatment of tumor diseases that has received growing interest in the past few years. In this study, we constructed liposomal photosensitizers (PS) for PDT by shoehorning as light-harvesting "antenna" molecules and dense [60]fullerene (C60) into lipid membrane bilayers. The liposomal PS showed improved photodynamic activity toward human cancer cells via the photoenergy transfer from photoactivated antenna molecules to C60.

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Nuclear spin coupling crossover in dense molecular hydrogen.

Project description:One of the most striking properties of molecular hydrogen is the coupling between molecular rotational properties and nuclear spin orientations, giving rise to the spin isomers ortho- and para-hydrogen. At high pressure, as intermolecular interactions increase significantly, the free rotation of H2 molecules is increasingly hindered, and consequently a modification of the coupling between molecular rotational properties and the nuclear spin system can be anticipated. To date, high-pressure experimental methods have not been able to observe nuclear spin states at pressures approaching 100 GPa (Meier, Annu. Rep. NMR Spectrosc. 94:1-74, 2017; Meier, Prog. Nucl. Magn. Reson. Spectrosc. 106-107:26-36, 2018) and consequently the effect of high pressure on the nuclear spin statistics could not be directly measured. Here, we present in-situ high-pressure nuclear magnetic resonance data on molecular hydrogen in its hexagonal phase I up to 123?GPa at room temperature. While our measurements confirm the presence of ortho-hydrogen at low pressures, above 70?GPa, we observe a crossover in the nuclear spin statistics from a spin-1 quadrupolar to a spin-1/2 dipolar system, evidencing the loss of spin isomer distinction. These observations represent a unique case of a nuclear spin crossover phenomenon in quantum solids.

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