Metallosupramolecular Assemblies Research Articles

Self-assembled Co(II) and Co(III) [M2L3] helicates and [M4L6] tetrahedra from an unsymmetrical quaterpyridine ligand.

In order to bind guest molecules with exquisite selectivity, biological host molecules often employ low symmetry binding pockets. The majority of metallosupramolecular assemblies, however, rely on symmetrical ligands to form high-symmetry assemblies that enclosing similarly symmetrical cavities. Here we employ an unsymmetrical quaterpyridine ligand in combination with cobalt(II) to form a mixture of low-symmetry [M2L3] helicates and [M4L6] tetrahedra and their subsequent oxidation to Co(III)-containing assemblies.

Architectural regulation of complexes for the design of metallo-supramolecular assemblies for visualizing dual-channel detection of CO

Metallo-supramolecular assembly (MSA) offers a prospective modulation tool for fabricating high-quality gas sensing platforms. However, visualizing multi-channel sensing of gaseous CO with high selectivity and sensitivity remains a formidable challenge. Here, we present a new strategy for the construction of MSA systems based on Pd(II) coordination bonds and host-guest interactions. The regulation of Pd(II) complexes is introduced into the design of MSA, and the photophysical properties, gelation behaviors, oscillatory mechanical characteristics, self-healing capabilities, and multi-stimuli responsiveness of the MSA systems can be easily modulated. The resulting two MSA systems, Pd/2BCN@6 and 2 Pd/2BCN@6, show great differences in sensing CO at solution-state (fluorescence change) and gel-state (gel-to-sol transition). Pd/2BCN@6-based gel provides a fast visual sensing (< 15 min) and efficient removal (∼15 %) of gaseous CO. 2 Pd/2BCN@6-based fluorescent system exhibits fast response (< 44 s), high selectivity and lower DLs: 7 ppm and 90.5 nM for gaseous CO and CORM-3, respectively.

Bioinspired Water Preorganization in Confined Space for Efficient Water Oxidation Catalysis in Metallosupramolecular Ruthenium Architectures.

ConspectusNature has established a sustainable way to maintain aerobic life on earth by inventing one of the most sophisticated biological processes, namely, natural photosynthesis, which delivers us with organic matter and molecular oxygen derived from the two abundant resources sunlight and water. The thermodynamically demanding photosynthetic water splitting is catalyzed by the oxygen-evolving complex in photosystem II (OEC-PSII), which comprises a distorted tetramanganese-calcium cluster (CaMn4O5) as catalytic core. As an ubiquitous concept for fine-tuning and regulating the reactivity of the active site of metalloenzymes, the surrounding protein domain creates a sophisticated environment that promotes substrate preorganization through secondary, noncovalent interactions such as hydrogen bonding or electrostatic interactions. Based on the high-resolution X-ray structure of PSII, several water channels were identified near the active site, which are filled with extensive hydrogen-bonding networks of preorganized water molecules, connecting the OEC with the protein surface. As an integral part of the outer coordination sphere of natural metalloenzymes, these channels control the substrate and product delivery, carefully regulate the proton flow by promoting pivotal proton-coupled electron transfer processes, and simultaneously stabilize short-lived oxidized intermediates, thus highlighting the importance of an ordered water network for the remarkable efficiency of the natural OEC.Transferring this concept from nature to the engineering of artificial metal catalysts for fuel production has fostered the fascinating field of metallosupramolecular chemistry by generating defined cavities that conceptually mimic enzymatic pockets. However, the application of supramolecular approaches to generate artificial water oxidation catalysts remained scarce prior to our initial reports, since such molecular design strategies for efficient activation of substrate water molecules in confined nanoenvironments were lacking. In this Account, we describe our research efforts on combining the state-of-the art Ru(bda) catalytic framework with structurally programmed ditopic ligands to guide the water oxidation process in defined metallosupramolecular assemblies in spatial proximity. We will elucidate the governing factors that control the quality of hydrogen-bonding water networks in multinuclear cavities of varying sizes and geometries to obtain high-performance, state-of-the-art water oxidation catalysts. Pushing the boundaries of artificial catalyst design, embedding a single catalytic Ru center into a well-defined molecular pocket enabled sophisticated water preorganization in front of the active site through an encoded basic recognition site, resulting in high catalytic rates comparable to those of the natural counterpart OEC-PSII.To fully explore their potential for solar fuel devices, the suitability of our metallosupramolecular assemblies was demonstrated under (electro)chemical and photocatalytic water oxidation conditions. In addition, testing the limits of structural diversity allowed the fabrication of self-assembled linear coordination oligomers as novel photocatalytic materials and long-range ordered covalent organic framework (COF) materials as recyclable and long-term stable solid-state materials for future applications.

Guest‐Shuttling in a Nanosized Metallobox

AbstractAn iridium‐conjoined long and narrow metallorectangle was obtained by combining a quinoxalinophenanthrophenazine‐connected Janus‐di‐imidazolylidene ligand and pyrazine. The size and shape of this assembly together with the fused polyaromatic nature of its panels provides it with properties that are uncommon for other metallosupramolecular assemblies. For example, this nanosized ‘slit‐like’ metallobox is able show very large binding affinities with planar organic molecules in such a way, that the cavity is asymmetrically occupied by the guest molecule. This unsymmetrical conformation leads to the existence of a large amplitude motion of these guests, which slide between the two sides of the cavity of the host, thus constituting rare examples of molecular shuttles.

Guest-Shuttling in a Nanosized Metallobox.

An iridium-conjoined long and narrow metallorectangle was obtained by combining a quinoxalinophenanthrophenazine-connected Janus-di-imidazolylidene ligand and pyrazine. The size and shape of this assembly together with the fused polyaromatic nature of its panels provides it with properties that are uncommon for other metallosupramolecular assemblies. For example, this nanosized 'slit-like' metallobox is able show very large binding affinities with planar organic molecules in such a way, that the cavity is asymmetrically occupied by the guest molecule. This unsymmetrical conformation leads to the existence of a large amplitude motion of these guests, which slide between the two sides of the cavity of the host, thus constituting rare examples of molecular shuttles.

Synthesis, characterisation and antimicrobial activity of supramolecular cobalt-peptide conjugates.

Herein, we describe the synthesis and characterisation of four new supramolecular cobalt conjugates of antimicrobial peptides functionalised with terpyridine ligands (L). Peptides were chosen based on the well-established arginine-tryptophan (RW)3 motif, with terpyridine-derivatized lysine (Lys(tpy)) added to the sequence, or replacing tryptophan residues. Self-assembly of the antimicrobial peptides with Co(BF4)2·6H2O formed exclusively CoL2 dimers (for peptides with one tpy ligand each) and Co2L4 metallo-macrocycles (for peptides with two tpy ligands for each peptide), which could be 'locked' by oxidation of Co(+II) to Co(+III) with ammonium ceric nitrate. The Co-peptide complexes were characterised by mass spectrometry and in solution by NMR spectroscopy, including 2D diffusion ordered NMR spectroscopy (DOSY) which confirmed the proposed stoichiometries. The antimicrobial activity of the novel peptides and their metallo-supramolecular assemblies was investigated by determination of their minimal inhibitory concentration (MIC) against a panel of Gram-positive and Gram-negative bacteria. Complexation with cobalt increases the activity of the peptides in almost every case. Most of the new metal-peptide conjugates showed good activity against Gram-positive bacteria, including a multi-resistant S. aureus strain and the opportunistic pathogenic yeast C. albicans (down to 7 μmol l-1 for the most active Co2L4 derivate), a value that is increased five-fold compared to the lysine-derivatized peptide ligand alone. Interestingly, conjugates of the CoL2 type also showed decent activity against Gram-negative bacteria including the WHO-flagged problematic A. baumannii strain (down to 18 μmol l-1 for the most active derivative).

Multi-functionalized Metallo-Supramolecular Spoked Wheels: Their Emission-Tunable Hierarchically Assembled System with Dye Molecules.

Supramolecular architectures with multiple emissive units are especially appealing due to their desired properties, such as artificial light harvesting and white-light emission. But fully achieving multi-wavelength photoluminescence in a single supramolecular architecture remains a challenge. In this paper, functionalized supramolecular architectures containing twelve metal centers and six pyrene moieties were nearly quantitatively synthesized by multi-component self-assembly and fully characterized by 1D and 2D nuclear magnetic resonance, dynamic light scattering, electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy. Moreover, the hierarchical nano-assemblies were prepared by introducing anionic dyes to the positively charged self-assembled framework, which contained three luminescence centers, namely, pyrene, tpy-Cd coordination parts, and Sulforhodamine B anions. Such a hierarchically assembled system displayed tunable emission by taking full advantage of aggregation-induced emission enhancement, aggregation-caused quenching, and fluorescence resonance energy transfer effects and showed the diverse emission colors. This research provides a new insight for constructing multiple emissive metallo-supramolecular assemblies.

Metal-N-Heterocyclic Carbene Chemistry Directed toward Metallosupramolecular Synthesis and Beyond.

ConspectusAs versatile, modular, and strongly coordinating moieties in organometallic compounds, N-heterocyclic carbenes (NHCs) have led to numerous breakthroughs in transition-metal catalysis, main group chemistry, and organocatalysis. In contrast, the chemistry of NHC-based metallosupramolecular assemblies, in which discrete individual components are held together via metal (M)-CNHC bonds, has been underdeveloped. Integrating NHCs into supramolecular assemblies would endow them with some unforeseen functions. However, one of the most critical challenges is seeking an appropriate combination of the rigid CNHC-M-CNHC units with the resulting topologies and applications. Toward this goal, for the last decade we have focused on the development of M-NHC directed toward metallosupramolecular synthesis. This Account aims to summarize our contributions to the application of M-NHC chemistry toward supramolecular synthesis from structural design to postassembly modification (PAM) and their functional applications since integrating NHCs into supramolecular assemblies has garnered much attention among organometallic, photochemical, and supramolecular researchers. While presenting representative examples of NHC-based architectures, we try to illustrate the purposes and concepts behind the systems developed to aid the rational approach to the design and fabrication of complex assemblies and M-NHC-templated photochemical reactions.We present synthetic approaches for new architectures by the rational design of starting NHC precursors, including the poly-NHC-based mechanically interlocked metallacages and the heteroleptic architectures based on electronic complementary and self-sorting mechanisms. The structural regulation of poly-NHC-based architectures with increasing topological complexity is elaborated on by selective combinations of tetraphenylethylene (TPE) units, NHC backbones, and N-wingtip substituents in a controllable manner.Subsequently, we move to elucidating an M-NHC-templated PAM approach that leads to functional organic cages featuring polyimidazolium/triazolium groups of different shapes and sizes that are difficult to access using alternative organic approaches. These organic cages possess well-defined cavities, and their in situ-generated NHC sites are ideal platforms for stabilizing metal nanoparticles (MNPs) within their cavities for improved catalytic performance.Finally, we demonstrate how to design supramolecular M-NHC templates to synthesize cyclobutane derivatives in homogeneous solutions in a catalytic fashion. Selected examples of M-NHC template-dependent structural transformations and photoreactions are discussed. Their applications in molecular recognition, aggregation-induced emission (AIE), cell imaging, anticancer activity, radical chemistry, and stimuli-responsive materials are also described.Taken together, M-NHC-templated approaches have proven to be powerful methods for constructing diverse architectures with functional applications. The development of this methodology is still in its infancy, with tremendous growth potential and a promising future. We believe that this Account will guide researchers to design fascinating and valuable M-carbene species for diverse applications.

Asymmetric triplex metallohelices stabilise DNA G-quadruplexes in promoter oncogene sequences and efficiently reduce their expression in cancer cells

Some metallo-supramolecular helical assemblies with size, shape, charge and amphipathic architectures similar to short cationic α-helical peptides have been shown to target and stabilise DNA G-quadruplexes (G4s) in vitro and downregulate the expression of G4-regulated genes in human cells. To expand the library of metallohelical structures that can act as efficient DNA G4 binders and downregulate genes containing G4-forming sequences in their promoter regions, we investigated the interaction of the two enantiomeric pairs of asymmetric Fe(II) triplex metallohelices with a series of five different DNA G4s formed by the human telomeric sequence (hTelo) and in the promoter regions of c-MYC, c-KIT, and k-RAS oncogenes. The metallohelices display preferential binding to G4s over duplex DNA in all investigated G4-forming sequences and induced arrest of DNA polymerase on template strands containing G4-forming sequences. Moreover, the investigated metallohelices suppressed the expression of c-MYC and k-RAS genes at mRNA and protein levels in HCT116 human cancer cells, as revealed by RT-qPCR analysis and western blotting.

Morphology Control of Supramolecular Assembly for Superior CO2Photoreduction

Coordination-driven metallo-supramolecular assemblies are potentially efficient catalysts in photocatalytic CO2 reduction. However, the relationship between morphology and photocatalytic performance remains barely explored. In this work, three metallo-supramolecular assemblies composed of Zn2+ and a flexible tris(terpyridine) ligand have been prepared for noble metal-free CO2 photoreduction on the basis of metal–ligand coordination, hydrogen bonding, and π–π stacking. The three assemblies possess distinct self-assembled morphologies including spherical particle, fibrous-like gel, and microrod. It has been found that the fibrous-like gel exhibits the best catalytic performance in photoreduction of CO2 to CO with a yield of 6.3 mmol g–1 h–1 and 94.7% selectivity over H2 generation. Photoelectrochemical measurements, photoluminescence quenching experiments, and UV–vis absorption spectroscopy studies have demonstrated that the ligand-based electron transfer of the gel is more efficient compared with the other two assemblies.

Morphology controlled Cu nanostructures grafted over rGO as highly efficient and recyclable heterogeneous catalysts to develop 1,2,3-triazole derivatives under click conditions

We report two easily synthesizable, reusable and morphology-controlled copper nanostructures grafted over rGO (i.e., rGO-CuNRs and rGO-CuNPs). The structure, morphology and the composition of the nanocatalysts have been characterized by TEM, SEM, XPS, PXRD and TGA analyses. These nanocatalysts having ‘rod-like’ (for rGO-CuNRs) as well as spherical (for rGO-CuNPs) nanostructures promoted one-pot multicomponent click reaction between in situ generated organic azide and phenyl acetylene to afford a 1,2,3-triazole derivative (L). The nanocomposites containing ‘rod-like’ morphology exhibited remarkably higher catalytic activity as compared to spherical nanoparticle counterparts. Interestingly, rGO-CuNRs exhibited rapid synthesis (∼ 60 min) of L with excellent yield (∼ 92%) involving pure water as a clean and eco-friendly reaction medium. A low copper loading, high recyclability upto 7 times with the negligible loss of catalytic activity and easy workup process is presented. The click product (L) will find promising applications as ‘polydentate click chelator’ to generate metallo-supramolecular assemblies in biomimetic chemistry.

Bi-directional geometric constraints in the construction of giant dual-rim nanorings.

In the field of metallo-supramolecular assemblies, supramolecular macrocycles have attracted considerable attention due to their guest recognition and catalytic properties. Herein, we report a novel strategy for the construction of giant hollow macrocyclic structures using a bi-directional geometric constraint strategy. We investigated the structural design of two terpyridine-based tetratopic organic ligands, whose inner and outer rims have different angles. Compared to conventional strategies of self-assembly using single angular orientation building blocks that typically generate small macrocyclic objects or polymers, the mutual interaction between the different angles of the ligands could promote the formation of giant hollow macrocyclic supramolecular architectures. The self-assembly mechanism and hierarchical self-assembly of giant supramolecular macrocycles have been characterized by NMR, ESI-MS and TEM experiments. The strategy used in this study not only advances the design of giant 2D macrocycles with large inner diameters but also gives insights into the mechanism of formation of large structures.

Remote stereocentres do not disrupt the stereochemical coupling in homochiral [M2L3] helicates and [M4L6] tetrahedra.

Despite the use of achiral ligands, the vast majority of metallosupramolecular assemblies containing octahedral tris-bidentate metal centres show strong stereochemical communication between metal centres, generally resulting in homochiral assemblies even though they are statistically disfavoured. Here we show that when resolved stereocentres are attached to the central part of a quaterpyridine ligand, the stereochemical coupling from this centre is insufficient to disrupt the strong stereochemical communication between metal centres in both [M2L3] helicates and [M4L6] tetrahedra.

Nonlinear shear rheology of single and double dynamics metal-ligand networks

We present a systematic experimental study of the shear rheology of metallosupramolecular assemblies based on entangled telechelic star polymers comprising one (single dynamic network) or two (double dynamics network) types of physical bonds with the aim to unravel the role of concentration and strength of these bonds on the nonlinear response. Model dynamic networks functionalized with terpyridine ligands were formed by adding different metal ions with increasing bonding strength, zinc, copper, and cobalt. The dynamics are driven by entanglement/disentanglement processes and a ligand exchange mechanism. Steady-state viscosities of single and double dynamics networks collapse onto a universal curve over a wide range of Weissenberg numbers based on terminal time (up to about 300 for single and 1000 for double), exhibiting stronger shear thinning (with an exponent of −0.76) compared to entangled neutral star polymers. Double dynamics networks consisting of two different metal ions (with different lifetimes) exhibit stronger mechanical coherence (rate-dependent fractional viscosity overshoot) and accumulate larger strain at steady-state flow compared to single-ion counterparts. The shear stress growth function signals exhibit weak, albeit unambiguous shear strain hardening, which becomes more pronounced for stronger associations. They also exhibit double overshoot, which reflects the interplay of association strength and chain deformation. Increasing the strength of associations leads to the failure of the Cox–Merz rule, which is more severe for single dynamic networks. The markedly different behavior of double dynamics networks is attributed to the fact that at sufficiently high ion content, the weaker bond acts as a sacrificial component, which provides local energy dissipation and enhances the overall deformability. This bears analogies with their linear viscoelastic response, which has revealed that the arm disentanglement (delayed due to the reversible bonds) effectively interpolates between the two single dynamic network components, depending on composition. Our results suggest ways to tailor the mechanical properties of this class of materials by judicious choice of the type and content of the ion.

Helicate versus Mesocate in Quadruple-Stranded Lanthanide Cages: A Computational Insight

To drive the synthesis of metallo-supramolecular assemblies (MSAs) and to fully exploit their functional properties, robust computational tools are crucial. The capability to model and to rationalize different parameters that can influence the outcome is mandatory. Here, we report a computational insight on the factors that can determine the relative stability of the supramolecular isomers helicate and mesocate in lanthanide-based quadruple-stranded assemblies. The considered MSAs have the general formula [Ln2L4]2− and possess a cavity suitable to allocate guests. The analysis was focused on three different factors: the ligand rigidity and the steric hindrance, the presence of a guest inside the cavity, and the guest dimension. Three different quantum mechanical calculation set-ups (in vacuum, with the solvent, and with the solvent and the dispersion correction) were considered. Comparison between theoretical and experimental outcomes suggests that all calculations correctly estimated the most stable isomer, while the inclusion of the dispersion correction is mandatory to reproduce the geometrical parameters. General guidelines can be drawn: less rigid and less bulky is the ligand and less stable is the helicate, and the presence of a guest can strongly affect the isomerism leading to an inversion of the stability by increasing the guest size when the ligand is flexible.

Metallosupramolecular Assemblies of Phthalocyanines, Subphthalocyanines and Bodipys: Photosensitizers for Visible-Light Induced Processes

Molecular self-assembly provides limitless possibilities to obtain stable and structurally well-defined supramolecules with different physicochemical properties than those of precursor building blocks. From all supramolecular interactions, strong and directional coordination-driven self-assembly allows a fine control over the rational design of two- and three-dimensional architectures with multiple potential applications. The preparation of cutting-edge metallo-supramolecular assemblies based on phthalocyanines, subphthalocyanines and BODIPYs is herein described. These ensembles have been applied for different purposes: i) as molecular receptors showing electronic interactions between the chromophore panels of the host and electroactive guests such as fullerenes and perylenediimides; ii) as hollow molecular containers able to influence a chemical reaction by providing an isolated cavity of particular size and shape, demonstrating, for example, the ability to induce unprecedented photoredox reaction with guest fullerenes, triggered by the porphyrinoid excited state; and iii) as metallosupramolecular amphiphilic systems, able to yield nanostructures via self-organization in aqueous media. Figure 1

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α'-Diimine Ligands.

The allosteric positive cooperativity accompanying the formation of compact [CuI(α,α′‐diimine)2]+ building blocks contributed to the historically efficient synthesis of metal‐containing catenates and knotted assemblies. However, its limited magnitude can easily be overcome by the negative chelate cooperativity that controls the overall formation of related polymetallic multistranded helicates and grids. Despite the more abundant use of analogous dioxygen‐resistant [AgI(α,α′‐diimine)2]+ units in modern entangled metallo‐supramolecular assemblies, a related thermodynamic justification was absent. Solid‐state structural characterizations show the successive formation of [AgI(α,α′‐diimine)(CH3CN)][X] and [AgI(α,α′‐diimine)2][X] upon the stepwise reactions of α,α′‐diimine=2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen) derivatives with AgX (X=BF4 −, ClO4 −, PF6 −). In room‐temperature, 5–10 mM acetonitrile solutions, these cationic complexes exist as mixtures in fast exchange on the NMR timescale. Spectrophotometric titrations using the unsubstituted bpy and phen ligands point to the statistical (=non‐cooperative) binding of two successive bidentate ligands around AgI, a mechanism probably driven by the formation of hydrophobic belts, that overcomes the unfavorable decrease in the positive charge borne by the metallic cation. Surprisingly, the addition of methyl groups adjacent to the nitrogen donors (6,6′ positions in dmbpy; 2,9 positions in dmphen) induces positive cooperativity for the formation of [Ag(dmbpy)2]+ and [Ag(dmphen)2]+, a trend assigned to additional stabilizing interligand interactions. Adding rigid and polarizable phenyl side arms in [Ag(Brdmbpy)2]+ further reinforces the positively cooperative process, while limiting the overall decrease in metal–ligand affinity.

Metallo-Supramolecular Complexation Behavior of Terpyridine- and Ferrocene-Based Polymers in Solution-A Molecular Hydrodynamics Perspective.

The contribution deals with the synthesis of the poly(methacrylate)-based copolymers, which contain ferrocene and/or terpyridine moieties in the side chains, and the subsequent analysis of their self-assembly behavior upon supramolecular/coordination interactions with Eu3+ and Pd2+ ions in dilute solutions. Both metal ions provoke intra and inter molecular complexation that results in the formation of large supra-macromolecular assembles of different conformation/shapes. By applying complementary analytical approaches (i.e., sedimentation-diffusion analysis in the analytical ultracentrifuge, dynamic light scattering, viscosity and density measurements, morphology studies by electron microscopy), a map of possible conformational states/shapes was drawn and the corresponding fundamental hydrodynamic and macromolecular characteristics of metallo-supramolecular assemblies at various ligand-to-ion molar concentration ratios () in extremely dilute polymer solutions were determined. It was shown that intramolecular complexation is already detected at (), while at solution/suspension precipitates. Extreme aggregation/agglomeration behavior of such dilute polymer solutions at relatively “high” metal ion content is explained from the perspective of polymer-solvent and charge interactions that will accompany the intramolecular complexation due to the coordination interactions.

Manipulating Assemblies in Metallosupramolecular Gels, Driven by Isomeric Ligands, Metal Coordination, and Adaptive Binary Gelator Systems.

Metallosupramolecular gel (MSG) is a unique combination of metal-ligand coordination chemistry and supramolecular gel chemistry with extraordinary adaptivity and softness. Such materials find broad uses in industry, pharmaceutical and biomedical sectors, and in technology generation among many others. Pyridyl-appended bis(urea) gelator systems have been extensively studied as potential MSG-forming materials in the presence of various metal ions. The previous molecular engineering approaches depicted competitive intermolecular and intramolecular binding modes involving urea and pyridyl groups and further fine-tuned by the presence of various molecular spacers. In those studies, formation of intermolecular hydrogen bonding among urea moieties to form urea tape was found to be the key factor in one-dimensional assembly and gel formation. In the present study, we show how two isomeric pyridyl-appended bis(urea) ligands can be designed appropriately to essentially eliminate the interference of competitive factors, leaving the intermolecular urea assembly practically unaffected even in the presence of metal ions. We found that one of the two ligands (L2) and the mixed ligand (L1 + L2) assemblies formed gel in the presence and absence of various metal ions. A metal ion with a linear coordination geometry significantly strengthened the gels. Moreover, an inherently weak L1 + L2 assembly appears to be more adaptive in accommodating larger metal ions especially with nonlinear coordination geometry preferences. Small-angle neutron scattering and rheological, spectroscopic, and morphological characterizations, collectively, capture a detailed interplay among ligand assembly, metal-ligand coordination, and adaptivity, driven by the pure versus mixed ligand assemblies. The knowledge gathered from the present study would be highly beneficial in engineering the metallosupramolecular polymeric assemblies toward their functional applications.

Post‐assembly modification of discrete poly‐NHC‐derived organometallic assemblies

The post‐assembly modification (PAM) of metallosupramolecular assemblies plays an important role in obtaining diverse architectures and expanding new functions. In this work, the trinuclear organometallic assemblies [Ag3(L)2](PF6)3 (L = 1a–c) were generated from the corresponding internal olefin‐bridged trisimidazolium, trisbenzoimidazolium, and trisimidazo[1,5‐ɑ]pyridinium salts H3‐L(PF6)3 (L = 1a–c) with Ag2O through coordination‐driven self‐assembly. Subsequently, complexes [Ag3(L)2](PF6)3 (L = 1a, 1b) were converted into corresponding gold(I) complexes [AuI3(L)2](PF6)3 (L = 1a, 1b) by transmetalation reaction. The oxidation addition of the gold(I) complexes [AuI3(L)2](PF6)3 (L = 1a, 1b) were carried out using iodine as an oxidant to give gold(III) complexes [AuIII3(L)2I6](PF6)3 (L = 1a, 1b). Irradiation of complexes [Ag3(L)2](PF6)3 (L = 1a, 1b) in solution leaded to structural transform into the corresponding cyclobutane‐bridged complexes [Ag3(L′)](PF6)3 (L′ = 2a, 2b) with quantitative yields.