Synthesis of a Dinuclear Platinum−Silver Complex Containing a Reactive Acetone Imine Prepared in Situ from Acetone and Ammonia and Stabilized by Metal Complexation

Casas, José M.; Forniés, Juan; Martín, and Antonio; Rueda, A.

doi:10.1021/om020197z

Cited by 20 publications

(7 citation statements)

References 37 publications

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“…In the HT sample, only Zn, C, N, and H remain in the material, yet again the increase in N content is notably high. Consequently, we believe only imines (ketimines and aldimines) without fluorine substitution remain, which are stabilized by interactions with the Zn 2+ sites, as has been shown with silver in the literature 54 . In fact, if the R′ group is not H, these molecules are specifically known as Schiff bases when they act as negatively charged ligands to form metal complexes 55 .…”

Section: [Emim]supporting

confidence: 56%

Ionic liquid facilitated melting of the metal-organic framework ZIF-8

et al. 2021

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Hybrid glasses from melt-quenched metal-organic frameworks (MOFs) have been emerging as a new class of materials, which combine the functional properties of crystalline MOFs with the processability of glasses. However, only a handful of the crystalline MOFs are meltable. Porosity and metal-linker interaction strength have both been identified as crucial parameters in the trade-off between thermal decomposition of the organic linker and, more desirably, melting. For example, the inability of the prototypical zeolitic imidazolate framework (ZIF) ZIF-8 to melt, is ascribed to the instability of the organic linker upon dissociation from the metal center. Here, we demonstrate that the incorporation of an ionic liquid (IL) into the porous interior of ZIF-8 provides a means to reduce its melting temperature to below its thermal decomposition temperature. Our structural studies show that the prevention of decomposition, and successful melting, is due to the IL interactions stabilizing the rapidly dissociating ZIF-8 linkers upon heating. This understanding may act as a general guide for extending the range of meltable MOF materials and, hence, the chemical and structural variety of MOF-derived glasses.

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Section: [Emim]supporting

confidence: 56%

Ionic liquid facilitated melting of the metal-organic framework ZIF-8

et al. 2021

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“…The pentafluorophenyl rings form dihedral angles of 62.6(6)° and 66.4(5)° with the platinum coordination plane, at the low end of the usual range for square planar pentafluorophenyl derivatives. 5,6,[42][43][44] The disposition of the pentafluorophenyl rings with respect to the platinum coordination plane impedes the formation of the binuclear derivative for steric reasons (see Chart 1).…”

Section: Synthesis and Characterization Of [Pt(c 6 F 5 ) 2 (Napy)] (1)mentioning

confidence: 99%

Hydrogen-bond mediation of supramolecular aggregation in neutral bis-(C₆F₅)Pt complexes with aromatic H-bond donating ligands. A synthetic and structural study

et al. 2004

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Six pentafluorophenylplatinum(II) complexes containing proton acceptor atoms (F) and pyridine-like aromatic ligands able to act as proton donors have been synthesized and characterized, with emphasis on the factors that mediate their supramolecular aggregation in the solid state--hydrogen bonds and pi-pi interactions. The crystal structure analyses of the mononuclear complexes cis-[Pt(C6F5)2(napy)](1), cis-[Pt(C6F5)2(CH2napy)](3), cis-[Pt(C6F5)2(2-ammpy)](5), and cis-[Pt(C6F5)2(2-bipym)](6) reveal the influence of D-HPt and D-HF (D=C, N) hydrogen bonding on the organization of molecules into stacks, which can be further interconnected to generate channels. The prevalence of hydrogen bonding over pi-pi interactions between aromatic rings in establishing the nature of the observed supramolecular aggregation is demonstrated.

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“…with silver in the literature. 53 In fact, if the R' group is not H, these molecules are specifically known as Schiff bases when they act as negatively charged ligands to form metal complexes. 54 For example, such an R' group could come be one of the ethyl/methyl groups that are lost from the EMIM cation, as shown by both the solution 1 H NMR and 13 C SS NMR.…”

Section: Resultsmentioning

confidence: 99%

Ionic Liquid Facilitated Melting of the Metal-Organic Framework ZIF-8

Nozari¹,

Calahoo²,

Tuffnell³

et al. 2021

Preprint

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<div>Hybrid glasses from melt-quenched metal-organic frameworks (MOFs) have been emerging as a new class of materials, which combine the functional properties of crystalline MOFs with the processability of glasses. However, only a handful of the vast variety of crystalline MOFs have been identified as being meltable. Porosity and metal-linker interaction strength have both been identified as crucial parameters in the trade-off between thermal decomposition of the organic linker and, more desirably, melting. For example, the inability of the prototypical zeolitic imidazolate framework (ZIF) ZIF-8 to melt, is ascribed to the instability of the organic linker upon dissociation from the metal center. Here, we demonstrate that the incorporation of an ionic liquid (IL) into the porous interior of ZIF-8 provides a means to reduce its melting temperature to below its thermal decomposition temperature (Tm < Td). Experimental evidence shows that the Tm of ZIF-8 obtained by IL infiltration is around 381 °C, and that the glass forming ability (Tg/Tm) of such melts is above 0.9, i.e. higher than those previously reported for other meltable MOFs. Our structural studies show that the prevention of decomposition, and successful melting, is due to the IL interactions stabilizing the rapidly dissociating ZIF-8 linkers upon heating. This understanding may act as a general guide for extending the range of meltable MOF materials and, hence, the chemical and structural variety of MOF-derived glasses.</div>

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Synthesis of a Dinuclear Platinum−Silver Complex Containing a Reactive Acetone Imine Prepared in Situ from Acetone and Ammonia and Stabilized by Metal Complexation

Cited by 20 publications

References 37 publications

Ionic liquid facilitated melting of the metal-organic framework ZIF-8

Ionic liquid facilitated melting of the metal-organic framework ZIF-8

Hydrogen-bond mediation of supramolecular aggregation in neutral bis-(C₆F₅)Pt complexes with aromatic H-bond donating ligands. A synthetic and structural study

Ionic Liquid Facilitated Melting of the Metal-Organic Framework ZIF-8

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Synthesis of a Dinuclear Platinum−Silver Complex Containing a Reactive Acetone Imine Prepared in Situ from Acetone and Ammonia and Stabilized by Metal Complexation

Cited by 20 publications

References 37 publications

Ionic liquid facilitated melting of the metal-organic framework ZIF-8

Ionic liquid facilitated melting of the metal-organic framework ZIF-8

Hydrogen-bond mediation of supramolecular aggregation in neutral bis-(C6F5)Pt complexes with aromatic H-bond donating ligands. A synthetic and structural study

Ionic Liquid Facilitated Melting of the Metal-Organic Framework ZIF-8

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Hydrogen-bond mediation of supramolecular aggregation in neutral bis-(C₆F₅)Pt complexes with aromatic H-bond donating ligands. A synthetic and structural study