Supramolecular polymers constructed by orthogonal self-assembly based on host–guest and metal–ligand interactions are attracting increasing attention currently because of their interesting properties and potential applications. Host–guest interactions impart these polymers with good selectivity and convenient enviro-responsiveness, and metal–ligand interactions endow them with various coordination geometries, strong yet tunable coordination binding abilities, as well as magnetic, redox, photophysical, and electrochromic properties. Therefore, supramolecular polymers constructed by orthogonal host–guest and metal–ligand interactions have wide applications in the fields of soft matter, fluorescence sensing, heterocatalysis, electronics, gas storage, etc. In this critical review, we will address the recent development of supramolecular polymeric systems involving metal–ligand interactions and host–guest molecular recognition. Specifically, we classify the related supramolecular polymers depending on the types of macrocyclic hosts, and highlight their intriguing properties originating from the elegant combination of host–guest complexation and metal centers.

Herein, a stimuli-responsive supramolecular metallogel was prepared by orthogonal coordination-driven self-assembly of a crown ether-based [3]pseudorotaxane and a 180° organic di-Pt(II) acceptor.

Three pseudorotaxanes consisting of a bis(p-phenylene)-34-crown-10-based cryptand host and 1,2-bis(4-pyridinium)ethane/ethylene derivative guests were obtained. It was found that small structural changes on guests could have a big effect on the binding behaviors of host–guest complexes.

A novel bis(m-phenylene)-32-crown-10 derivative bearing two π-extended pyridyl groups was synthesized, and its host–guest complexation with a paraquat derivative to form a threaded [2]pseudorotaxane was studied. Subsequently, a poly[2]pseudorotaxane was constructed with a metallosupramolecular polymer backbone via metal coordination, which was comprehensively confirmed by the combination of 1H NMR, 31P{1H} NMR, DOSY NMR, DLS, and EDX techniques.

The themes of coordination-driven self-assembly, host–guest interactions, and supramolecular polymerization are unified in an orthogonal noninterfering fashion to deliver side-chain poly[2]pseudorotaxanes. Specifically, a bis(p-phenylene)-34-crown-10 derivative 1 bearing two pyridyl groups polymerizes into a side-chain poly[2]pseudorotaxane upon the addition of di-Pt(II) acceptor 4 in the presence of paraquat. Interestingly, by adding a competitive guest 3, the poly[2]pseudorotaxane can realize a conversion in one pot.

Herein, a cation responsive linear supramolecular polymer was constructed in an orthogonal fashion by unifying the themes of coordination-driven self-assembly and cryptand-based host–guest interaction.

Facile and efficient design and control of the topologies of polymers are important in the field of supramolecular polymers. Different pre-organized supramolecular coordination complexes with secondary recognition moieties in various directions can be easily obtained by just changing the number or orientation of the coordination sites. Herein, a responsive cross-linked supramolecular polymer network was constructed in an orthogonal way by unifying the themes of coordination-driven self-assembly and cryptand-based molecular recognition. Two stepwise self-assembly behaviors as well as a one-pot interaction for the preparation of this advanced supramolecular polymer were addressed. Notably, cation-induced dynamic properties make the resulting polymer promising candidate for application in degradable materials.

Two B21C7-based [1]rotaxanes were synthesized in high yields by means of copper(II)-mediated Eglinton coupling and a subsequent Pd/C-catalyzed reduction under H2. X-ray single-crystal analysis shows that [1]rotaxane takes on a self-entangled conformation, wherein the macrocycle is threaded by its own tail. Moreover, it was found that [1]rotaxane with a flexible skeleton had more rotational motions than that of one with a rigid skeleton.

A novel bis(m-phenylene)-32-crown-10-based cryptand 1 with a pyridine nitrogen atom outside on the third arm was designed and synthesized. Subsequently, host–guest complexation between cryptand 1 and a selection of bipyridinium guests has been studied. More interestingly, the [3]pseudorotaxane 2⊃52 was obtained in three methods by utilizing the noninterfering orthogonal nature of coordination-driven self-assembly and host–guest interactions.

Host–guest complexation between a dibenzo-24-crown-8-based cryptand and a paraquat derivative was studied. Subsequently, two novel [2]rotaxanes based on the dibenzo-24-crown-8-based cryptand/paraquat recognition motif were prepared by threading-followed-by-stoppering method and single-pot method, respectively. The obtained mechanically interlocked structures were confirmed by 1H NMR, 13C NMR, 2D NMR, and ESI-MS.

Herein, a stimuli-responsive supramolecular metallogel was prepared by orthogonal coordination-driven self-assembly of a crown ether-based [3]pseudorotaxane and a 180° organic di-Pt(II) acceptor.

Supramolecular polymers constructed by orthogonal self-assembly based on host–guest and metal–ligand interactions are attracting increasing attention currently because of their interesting properties and potential applications. Host–guest interactions impart these polymers with good selectivity and convenient enviro-responsiveness, and metal–ligand interactions endow them with various coordination geometries, strong yet tunable coordination binding abilities, as well as magnetic, redox, photophysical, and electrochromic properties. Therefore, supramolecular polymers constructed by orthogonal host–guest and metal–ligand interactions have wide applications in the fields of soft matter, fluorescence sensing, heterocatalysis, electronics, gas storage, etc. In this critical review, we will address the recent development of supramolecular polymeric systems involving metal–ligand interactions and host–guest molecular recognition. Specifically, we classify the related supramolecular polymers depending on the types of macrocyclic hosts, and highlight their intriguing properties originating from the elegant combination of host–guest complexation and metal centers.

Herein, a cation responsive linear supramolecular polymer was constructed in an orthogonal fashion by unifying the themes of coordination-driven self-assembly and cryptand-based host–guest interaction.