Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox product

Greatorex, Sam; Vincent, Kevin B.; Baldansuren, Amgalanbaatar; McInnes, Eric J. L.; Patmore, Nathan J.; Sproules, Stephen; Halcrow, Malcolm A.

doi:10.1039/c8cc10122a

Cited by 4 publications

(2 citation statements)

References 39 publications

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“…Synthesis of the host TBTQ-(OG) 6 . The sugar-functionalized host TBTQ-(OG) 6 was synthesized starting from the known compound TBTQ-(OH) 6 ( Scheme 1 ) [ 31 – 33 ]. The reaction of TBTQ-(OH) 6 with propargyl bromide in the presence of potassium carbonate gave the hexakis-propargyl ether, TBTQ-(OP) 6 , in 31% yield.…”

Section: Resultsmentioning

confidence: 99%

“…All these TBTQ-based hosts were found to bind fullerenes in organic solvents with different strengths, as indicated by UV–vis or 1 H NMR titration experiments. Moreover, easily accessible C 3 v -symmetrical sixfold hydroxy-functionalized TBTQ derivatives gain increasing attention for potential applications in host–guest recognition, such as gas storage and cationic complexation [ 31 – 33 ].…”

Section: Introductionmentioning

confidence: 99%

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Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

Liu¹,

Wang²,

Li³

et al. 2020

Beilstein J. Org. Chem.

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A sugar-functionalized water-soluble tribenzotriquinacene derivative bearing six glucose residues, TBTQ-(OG) 6 , was synthesized and its interaction with C60 and C70-fullerene in co-organic solvents and aqueous solution was investigated by fluorescence spectroscopy and ultraviolet-visible spectroscopy. The association stoichiometry of the complexes TBTQ-(OG) 6 with C60 and TBTQ-(OG) 6 with C70 was found to be 1:1 with binding constants of K a = (1.50 ± 0.10) × 105 M−1 and K a = (2.20 ± 0.16) × 105 M−1, respectively. The binding affinity between TBTQ-(OG) 6 and C60 was further verified by Raman spectroscopy. The geometry of the complex of TBTQ-(OG) 6 with C60 deduced from DFT calculations indicates that the driving force of the complexation is mainly due to the hydrophobic effect and to host–guest π–π interactions. Hydrophobic surface simulations showed that TBTQ-(OG) 6 and C60 forms an amphiphilic supramolecular host–guest complex, which further assembles to microspheres with diameters of 0.3–3.5 μm, as determined by scanning electron microscopy.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

Liu¹,

Wang²,

Li³

et al. 2020

Beilstein J. Org. Chem.

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Donor‐Acceptor Tribenzotriquinacene‐Based Molecular Wizard Hats Bearing Three ortho‐Benzoquinone Units

Hung

Kuck

Chow

2023

Chemistry A European J

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Two π-extended bay-bridged tribenzotriquinacenes ("TBTQ wizard hats") 12 and 16 bearing three mutually conjugated, alternating veratrole-type and ortho-benzoquinone units were synthesized. The electronic properties of these complementarily arranged, nonplanar push-pull systems are affected by the fusion with the rigid, C 3 -symmetric TBTQ core to a different extent, as revealed by X-ray structural analysis, UV-vis spectroscopy and cyclovoltammetry. The combination of three quinone units within the original TBTQ core and three veratrole-type bay bridging units in 12 gives rise to a more efficiently π-conjugated chromophore, as reflected by the shallower shape of wizard hat and its absorption in the visible up to 750 nm in comparison to 16. Congener 12 contains an aromatic 18-π electron system in contrast to the cross-conjugated analog 16. X-ray structure analysis of the precursor dodecaether 15 revealed the formation of a cage-like supramolecular dimer, in which the peripheral dioxane-type ether groups interlace by twelve noncovalent CÀ H•••••O bonds.

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Benzoannellated Fenestranes Bearing para‐Terphenyl Units

2021

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In memory of Klaus HafnerThe synthesis of several centrotriindanes bearing ortho-phenyl groups in the sterically constricted bay regions is described. The classical three-step sequence including twofold cyclodehydration of the corresponding 2,2-dibenzyl-1,3-indanediols afforded an angular difuso-triidane and several all-cis-tribenzo[5.5.5.6] fenestranols equipped with two or four ortho-phenyl groups. In contrast to the construction of these conformationally flexible centrotriindanes, attempts to synthesize ortho,ortho-diphenyl-substituted tribenzotriquinacenes failed due to the increased rigidity of the TBTQ skeleton. The high steric load imposed by the para-terphenyl moieties affects the spirocyclization between 1,3-indanedione and 1,5-di-(para-2'-terphenylyl)pentadienone, kinetic control of which is critical to access the all-cis-tribenzo [5.5.5.6]fenestrane framework. In contrast, the corresponding tetraphenyl-cis,cis,cis,trans-tribenzo[5.5.5.6]fenestranol is easily accessible.

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Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox product

Abstract: One-electron oxidation of the compound shown shows no evidence for intervalence charge transfer in the macrocylic ligand radical product. In contrast, related [{Pt(L)}3(μ3-ctc˙)]+ (H6ctc = cyclotricatechylene), exhibits class II mixed valency.

Cited by 4 publications

References 39 publications

Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

Donor‐Acceptor Tribenzotriquinacene‐Based Molecular Wizard Hats Bearing Three ortho‐Benzoquinone Units

Benzoannellated Fenestranes Bearing para‐Terphenyl Units

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