Probing the structural and electronic response of Magnus green salt compounds [Pt(NH2R)4][PtCl4] (R = H, CH3) to pressure

Richardson, Jonathan; Benjamin, Helen; Moggach, Stephen A.; Warren, Lisette R.; Warren, Mark R.; Allan, David R.; Saunders, Lucy K.; Morrison, Carole A.; Robertson, Neil

doi:10.1039/d0cp03280h

Cited by 3 publications

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“…Stronger interlayer ligand•••ligand interactions increased the amount of dispersion in the conduction band, which facilitated a much faster band gap narrowing in these compounds than in, for example, the Magnus green salts, where much flatter ligandbased conduction bands were exhibited. 27 As part of a wider study comparing the structural and property responses of pressure-responsive platinum-containing complexes, we have prepared a derivative complex of [Pt(bqd) 2 ], in which two hydrogen atoms on each phenyl ring of the 1,2-dioximato ligand are replaced by n-butyl chains (Fig 1, hereafter [Pt(bqd-dibutyl) 2 ]). These modifications were undertaken to enhance the solubility of the complex and thus improve its processability to be applied as a thin film in transistors or other molecular-electronic devices.…”

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Evaluating the crystalline orbital hierarchy and high-pressure structure–property response of an extended-ligand platinum(ii) bis(1,2-dioximato) complex

et al. 2021

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confidence: 99%

Evaluating the crystalline orbital hierarchy and high-pressure structure–property response of an extended-ligand platinum(ii) bis(1,2-dioximato) complex

et al. 2021

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Metallophilic interactions

Doerrer

Rosario²,

Fan³

2023

Comprehensive Inorganic Chemistry III

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The curious case of proton migration under pressure in the malonic acid and 4,4′-bipyridine cocrystal

Patyk-Kaźmierczak,

Izquierdo-Ruiz,

Lobato

et al. 2024

Int Union Crystallogr J

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In the search for new active pharmaceutical ingredients, the precise control of the chemistry of cocrystals becomes essential. One crucial step within this chemistry is proton migration between cocrystal coformers to form a salt, usually anticipated by the empirical ΔpK a rule. Due to the effective role it plays in modifying intermolecular distances and interactions, pressure adds a new dimension to the ΔpK a rule. Still, this variable has been scarcely applied to induce proton-transfer reactions within these systems. In our study, high-pressure X-ray diffraction and Raman spectroscopy experiments, supported by DFT calculations, reveal modifications to the protonation states of the 4,4′-bipyridine (BIPY) and malonic acid (MA) cocrystal (BIPYMA) that allow the conversion of the cocrystal phase into ionic salt polymorphs. On compression, neutral BIPYMA and monoprotonated (BIPYH+MA−) species coexist up to 3.1 GPa, where a phase transition to a structure of P21/c symmetry occurs, induced by a double proton-transfer reaction forming BIPYH2 2+MA2−. The low-pressure C2/c phase is recovered at 2.4 GPa on decompression, leading to a 0.7 GPa hysteresis pressure range. This is one of a few studies on proton transfer in multicomponent crystals that shows how susceptible the interconversion between differently charged species is to even slight pressure changes, and how the proton transfer can be a triggering factor leading to changes in the crystal symmetry. These new data, coupled with information from previous reports on proton-transfer reactions between coformers, extend the applicability of the ΔpK a rule incorporating the pressure required to induce salt formation.

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Probing the structural and electronic response of Magnus green salt compounds [Pt(NH₂R)₄][PtCl₄] (R = H, CH₃) to pressure

Abstract: Despite possessing the desirable crystal packing and short Pt⋯Pt stacking distances required for a large piezoresistive response, we explain why the conductivity-pressure response of the Magnus green salt [Pt(NH3)4][PtCl4] is extremely sluggish.

Cited by 3 publications

References 65 publications

Evaluating the crystalline orbital hierarchy and high-pressure structure–property response of an extended-ligand platinum(ii) bis(1,2-dioximato) complex

Evaluating the crystalline orbital hierarchy and high-pressure structure–property response of an extended-ligand platinum(ii) bis(1,2-dioximato) complex

Metallophilic interactions

The curious case of proton migration under pressure in the malonic acid and 4,4′-bipyridine cocrystal

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