Covalent Post-assembly Modification Triggers Structural Transformations of Borromean Rings

Abstract

Experimental procedures, spectroscopic data, and X-ray crystallography (PDF) X-ray data for 1 (CCDC 1901497) (CIF) X-ray data for 2 (CCDC 1901498) (CIF) X-ray data for 3-BR (CCDC 1901499) (CIF) X-ray data for 5 (CCDC 1901500) (CIF) X-ray data for 6 (CCDC 1901501) (CIF) X-ray data for 7 (CCDC 1901502) (CIF)

Post‐Metalation Modification of a Macrocyclic Dicobalt(III) Metallohost by Site‐Selective Ligand Exchange for Guest Recognition Control

“…In order to use the ligand exchange for the post-synthetic modification of responsive host molecules, we have to employaparent host framework that is stableu nder the conditions used for the modification, whereas self-assembledc ages sometimes undergo ligand exchange in the skeletal coordination bonds which leads to an undesired disruption of the host structure and/or size conversion such as cage-to-cage transformations. [9] Therefore, the host structures for post-synthetic modification based on ligand exchange should contain two kinds of coordination bonds;o ne is sufficiently inert to firmly hold the metali onsi nthe structure and the other is sufficiently labile to enablet he ligand exchange for the post-syntheticm odification. [10] Chelatec oordination sites incorporated in af ully organic framework may also be usefult oh old metal ions, on whichagreaterv ariety of modifiers can be introducedb yc oordination bonds.…”

Dynamic Interconversion between Solomon Link and Trapezoidal Metallacycle Ensembles Accompanying Conformational Change of the Linker

“…In order to study the kinetics of the conversion of Solomon link 1 into metallarectangle 2 , a 60 m m (with respect to Cp*Rh) solution of 1 in CD 3 OD was diluted to around 1.0 m m and monitored by quantitative 1 H NMR experiments (Figure S21). Linear regression analysis of the experimental data (Figure S22) showed that the conversion process could be well fitted by the rate law of a first‐order reaction, giving a conversion reaction rate coefficient of k =0.0493 min −1 at 298 K with an adjusted R 2 value of 0.9911, as shown in Table S1.…”

“…The resultsi ndicatedt hat the self-assembly favors the formation of Solomonl ink 1 at higher concentrations, whereas at lower concentrations the equilibrium shifts in favor of trapezoidal metallacycle 2.I no rder to study the kineticso ft he conversion of Solomonl ink 1 into metallarectangle 2,a6 0mm (with respectt oC p*Rh) solutiono f1 in CD 3 OD was diluted to around1 .0 mm and monitored by quantitative 1 HNMR experiments ( Figure S21). Linear regression analysiso ft he experimental data ( Figure S22) showedt hat the conversion process could be well fitted by the rate law of af irst-order reaction, [15] giving ac onversion reaction rate coefficient of k = 0.0493 min À1 at 298 Kw ith an adjusted R 2 value of 0.9911, as shown in Ta ble S1.…”

Guest‐Reaction Driven Cage to Conjoined Twin‐Cage Mitosis‐Like Host Transformation

“…Assembled supramolecular architectures offer a controllable platform at the molecular level to mimic the function of biosystems [3] . Adaptive transformations have also been widely seen in such artificial hosts with stimuli‐responsiveness to anion, [4] solvent, [5] concentration, [5a, 6] stoichiometric ratio of components, [5f, 7] post‐modification [6b, 8] chemical fuel, [9] and so on [5f, 10] . Guided by the induced‐fit mechanism, guest‐templated synthesis offers an important route toward otherwise inaccessible complicated host–guest complexes [5f, 11] .…”