Spontaneous Synthesis of [FeII(Atrz)3]SO4 and its Analogues Through Accelerated Ageing: New Insights from Small‐Scale Reactions

Lonergan, Rhona F.; Conway, Georgina A.; Doheny, Patrick W.; Shepherd, Helena J.

doi:10.1002/chem.202201823

Cited by 4 publications

(1 citation statement)

References 60 publications

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“…This reaction in many respects resembles humidity-accelerated aging reactions. 30,31 The pBq:2Ct complex obtained in this way over several weeks was in the form of single crystals, up to 0.3 mm in size. They are orange plates and prisms.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Charge-Transfer Benzoquinone:Catechol Complexes, Their Aging Reactions, High-Pressure Polymorphs and Skew Pancake Bonds

Rusek

Katrusiak

2023

J. Phys. Chem. C

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Charge-transfer complexes are the key elements of optoelectronic devices. Quinhydrone (Qh) was the first discovered charge-transfer complex, and for its structure, the π-stacking and pancake bonds were identified. Later, the atom-over-atom criterion was added to the pancake-bond definition. However, this feature is absent in the structures of both Qh polymorphs. Here, we report new charge-transfer complexes of para-benzoquinone (pBq) and catechol (Ct), the only unknown isomers of Qh. Compounds pBq and Ct preferentially co-crystallize to a 1:1 brown complex, α-pBq:Ct, with the molecules alternatively stacked into columns. We have revealed the accelerated aging reaction of α-pBq:Ct, leading to an orange pBq:2Ct complex, the only representative of the 1:2 stoichiometry for the complexes of pBq with isomeric hydroquinone (Hq), resorcinol (Rs), and Ct. On compression to 1.5 GPa, α-pBq:Ct undergoes a transition converting the catechol conformers syn into anti in a markedly darker new phase β-pBq:Ct. This conversion extensively extends the transition hysteresis between phases αand β-pBq:Ct. At about 2.5 GPa, a radical complex γ-pBq:Ct is formed, which starting from 3.0 GPa gradually transforms into the black amorphous phase δ-pBq:Ct. In phase α-pBq:2Ct, both Ct-conformers syn and anti are present, but high pressure induces a phase transition, eliminating conformers syn in a much darker new phase, β-pBq:2Ct. High pressure reduces the energy band gap of all pBq:Ct and pBq:2Ct phases. The skew geometry of pancake bonds associated with p−p interactions is common for all Qh, pBq:Rs, pBq:Ct, and pBq:2Ct complexes.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Charge-Transfer Benzoquinone:Catechol Complexes, Their Aging Reactions, High-Pressure Polymorphs and Skew Pancake Bonds

Rusek

Katrusiak

2023

J. Phys. Chem. C

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Spontaneous Synthesis of [Fe^II(Atrz)₃]SO₄ and its Analogues Through Accelerated Ageing: New Insights from Small‐Scale Reactions

Lonergan

Conway

Doheny

et al. 2022

Chemistry A European J

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Accelerated ageing reactions that take place between two solid materials on contact in the absence of added solvent have been used to synthesise two spin-crossover-active 1D coordination polymers and one of their Cu(II) analogues. The hygroscopy of the ligands and the relative humidity of the reaction chamber have been shown to be particularly important factors in the rate of reaction. Small-scale reactions between a few individual crystals have allowed observation of deliquescence of the 4-aminotriazole ligand at high humidity. The metal salt does not dissolve, and the ligand diffuses into the crystal of the metal salt during the reaction. In the case of the Cu analogue, the formation of the product causes the crystal of the metal salt to deform with the formation of pseudocrystals, which have a fibrous structure.

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A cationic Co(II) coordination polymer 1∞[Co(µ-L)(µ-Cl)(H2O)2]+ with the 4-amino-4H-1,2,4-triazole ligand: Structure, thermal behavior, and antimicrobial activity

Hassen

Arfaoui

Filinchuk

et al. 2023

Inorganica Chimica Acta

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Spontaneous Synthesis of [Fe^II(Atrz)₃]SO₄ and its Analogues Through Accelerated Ageing: New Insights from Small‐Scale Reactions

Cited by 4 publications

References 60 publications

Charge-Transfer Benzoquinone:Catechol Complexes, Their Aging Reactions, High-Pressure Polymorphs and Skew Pancake Bonds

Charge-Transfer Benzoquinone:Catechol Complexes, Their Aging Reactions, High-Pressure Polymorphs and Skew Pancake Bonds

Spontaneous Synthesis of [Fe^II(Atrz)₃]SO₄ and its Analogues Through Accelerated Ageing: New Insights from Small‐Scale Reactions

A cationic Co(II) coordination polymer 1∞[Co(µ-L)(µ-Cl)(H2O)2]+ with the 4-amino-4H-1,2,4-triazole ligand: Structure, thermal behavior, and antimicrobial activity

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