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Coordination chemistry

CH···anion bonds that template zinc molecular knots

Bilbeisi RA, Prakasam T, Lusi M, et al. · Chemical science · 2016

Open access · cc by · source: Europe PMC

Weak C–H···anion contacts in water/methanol steer a Zn(II) dynamic library toward a trefoil knot that binds two bromides in its cavity.

Study at a glance

Design
Other — Zn(II)-templated DFP/DAB assemblies (catenane/knot/link) with aqueous anion-binding studies
N
Supramolecular synthesis and binding — no sample N
Population
DFP–DAB–Zn(II) interlocked assemblies in MeOD/D2O
Outcome
CH···anion-mediated topology selection and aqueous anion binding

Structured fields used in claim comparison tables when every cited study has a complete layer.

Key findings

CH···anion interactions in MeOD/D2O mediate topology. Solid-state TK6+ holds two bromides via bipyridinyl C–H hydrogen bonds. Cavity ~130 Å3 fits two anions ≤2.5 Å. DFT dipole is 2.77 D (gas) and 4.97 D (water). TK6+ still binds anions in D2O.

Methodology

Authors assembled DFP + DAB with Zn(II), used anion templation and temperature to bias [2]catenane, trefoil knot TK6+ and Solomon link, solved TK6+ crystals with two bromides, computed ESP/dipole, and studied aqueous anion binding by NMR.

Limitations

A full aqueous Kd table for every anion under physiological salt is incomplete; TFA association mode could not be assigned by HOESY.

How this study connects

Role on claims

Each row is a claim on a concept or method page where this paper supports, challenges, or qualifies the statement. Roles are hand-checked — not a model guess.

  • SupportsCoordination chemistryconcept

    This library holds 8 empirical chemistry papers on coordination chemistry with isolated findings, rates or spectra rather than reviews.

    Evidence for the claim as stated.

  • SupportsCoordination chemistryconcept

    Weak C–H···anion contacts in water/methanol steer a Zn(II) dynamic library toward a trefoil knot that binds two bromides in its cavity.

    Evidence for the claim as stated.

  • SupportsCoordination chemistryconcept

    A crystal structure is a snapshot; solution speciation and fluxional ligands can differ.

    Evidence for the claim as stated.

Open questions

Tensions this paper is part of

From concept pages' “where studies disagree.” Disagreement means the same question; scope means different assays, populations, or outcomes.

Related papers in this topic

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