Can Coordination‐Driven Supramolecular Self‐Assembly Reactions Be Conducted from Fully Aliphatic Linkers?

Abstract

The reaction between a preassembled Cu bimetallic molecular clip with a short intermetallic distance and a series of fully aliphatic cyano-capped ditopic linkers with increasing lengths was investigated. It is shown that, depending on the length of the ditopic linkers, the rational design of unprecedented supramolecular compact metallacycles containing fully aliphatic walls is possible. The specific preorganized molecular arrangement of the molecular clip used favors stabilizing interlinker London dispersion interactions, which allow, as the length of the linkers increases, the selective formation of discrete compact metallacycles at the expense of 1D coordination polymers. The generalizability of this approach was demonstrated by the reaction of fully aliphatic cyano-capped linkers with two other types of preassembled Cu bimetallic molecular clips that also had short intermetallic distances.

Adaptive Coordination-Driven Supramolecular Syntheses toward New Polymetallic Cu(I) Luminescent Assemblies

“…Due to specific molecular design, some Cu­(I) bimetallic precursors bearing short intermetallic distances and conformationally stable coordination directions have been identified as versatile preorganized precursors . Very specific CDS toward compact supramolecular metallacycles could thus be conducted, including the one-step quantitative preparation of the blue luminophor consisting of tetrametallic Cu­(I) compact metallacycle A (Figure a) …”

Die Dreikomponenten‐Selbstorganisation ändert ihre Richtung: Ein Sprung von einfachen Polymeren zu 3D‐Netzwerken sphärischer Wirt/Gast‐Aggregate

“…Zur Verknüpfung dieser in situ gebildeten Supramoleküle wurden die flexiblen aliphatischen Dinitrile NC(CH 2 ) x CN (DNx, x = 1-10) ausgewählt, da ihre Koordinationschemie mit Silbersalzen bereits Gegenstand von Untersuchungen war. [15] Hier berichten wir über ein steuerbares Dreikomponenten-Selbstorganisationssystem,d as entweder zu CPs oder zu supramolekularen CPs,d ie Wirt/Gast-fähige Knoten enthalten, führt. Während dieser Untersuchung wurde das Phänomen des dramatischen Wechsels des Selbstorganisationspfades von einem CP hin zu einem supramolekularen CP entdeckt:B ei DNx mit x = 1-6 führt die Selbstorganisation zu einfachen CPs,w enn allerdings von x !…”

Three‐Component Self‐Assembly Changes its Course: A Leap from Simple Polymers to 3D Networks of Spherical Host–Guest Assemblies

“…[14] To use these supramolecular aggregates as hosting nodes joined in apolymeric structure it is necessary to provide coordination sites at the metal cations for the additional linkers,w hich should be longer than the van der Waals contact of the supramolecules.M oreover,t he desired polymer of supramolecules should be accessible via aone-pot self-assembly.F or this purpose we have chosen the silver salt with the non-coordinating anion SbF 6 À ,which in the reaction with polyphosphorus ligand A would be able to form fullerene-like host-guest able supramolecules bearing free coordination sites at the silver centers.T ol ink these in situ generated supramolecules,t he flexible aliphatic dinitriles NC(CH 2 ) x CN (DNx, x = 1-10) were selected as their coordination chemistry with silver salts has already been investigated. [15] Herein we report on acontrollable three-component selfassembly system, leading either to CPs or to supramolecular CPs containing host-guest able nodes.D uring this study ap henomenon of the dramatic change of the self-assembly course from CP to supramolecular CP was discovered:F or DNx with x = 1-6, the self-assembly leads to simple CPs, while starting from x ! 7, the self-assembly suddenly leaps towards the formation of supramolecular CPs,o nly sporadically accompanied by CPs as minor products.T he resulting supramolecular CPs are obtained in one-pot reactions in high yields and the supramolecular nodes are convenient for further implementation in host-guest chemistry.…”