Supramolecular Coordination Research Articles

Hierarchical self-assembly induced supramolecular polymer helical nanowires with white circularly polarized luminescence.

Novel CPL-active supramolecular helical nanowires (SHNWs) were successfully constructed, via the hierarchical self-assembly of supramolecular coordination polymers. The CPL colors of the resultant SHNWs are drastically regulated from blue to red, and pass through white.

Mitochondria-targeted supramolecular coordination container encapsulated with exogenous itaconate for synergistic therapy of joint inflammation.

Rationale: Inflammatory macrophages and osteoclasts (OCs) play critical roles in joint inflammation, which feature the excessive production of reactive oxygen species (ROS), resulting in synovial inflammation and bone erosion. Scavenging ROS, especially by modulating mitochondrial metabolic activity, could be a desirable strategy for the management of inflammatory joints. This study aimed to develop a mitochondria-targeted supramolecular drug delivery system with exogenous and endogenous ROS-scavenging activities for the treatment of joint inflammation.Methods: In this study, we utilized a zinc-based metal-organic supercontainer (MOSC) as a proton sponge and electron reservoir with outstanding proton binding capacity, extracellular ROS-scavenging ability, and biocompatibility to establish an efficient supramolecular nanocarrier for endo/lysosomal escape and mitochondrial targeting. 4-Octyl itaconate (4-OI), an itaconate derivative, served as the loaded guest for the construction of a synergistic therapeutic system for inflammatory macrophages and OCs.Results: After the effective encapsulation of 4-OI, 4-OI@Zn-NH-pyr not only exhibited potent ROS-scavenging capacity, but also reduced ROS production by mediating mitochondrial respiration in inflammatory macrophages. Regarding its anti-inflammatory efficacy, 4-OI@Zn-NH-pyr ameliorated the inflammatory reaction by activating nuclear factor erythroid 2-related factor 2 (Nrf2), thus increasing the production of antioxidants, apart from the inhibition of NF-κB pathways. Additionally, receptor activator of nuclear factor-κB ligand (RANKL)-induced osteoclast differentiation and function was remarkably suppressed by 4-OI@Zn-NH-pyr. Consistent with in vitro observations, 4-OI@Zn-NH-pyr efficiently inhibited synovial inflammation and subchondral bone destruction in an acute arthritis model.Conclusion: By using MOSCs that are highly reactive to ROS as drug-loaded matrices for the first time, this study provides an avenue for the management of severe joint inflammation by designing synergistic supramolecular drug-delivery systems with subcellular targeting and ROS-scavenging capacity.

Highly Efficient Bifunctional Catalyst with 2d Mon Formed in Situ Synergy for Oer and Orr Based-On Coii Doped Moiv-Niii Supramolecular Coordination Polymer

Highly Efficient Bifunctional Catalyst with 2d Mon Formed in Situ Synergy for Oer and Orr Based-On Coii Doped Moiv-Niii Supramolecular Coordination Polymer

Stereoselective formation of bismuth complexes by transmetalation of lead with adaptable overhanging carboxylic acid 5,10-strapped porphyrins

Out-of-plane deformations of metalloporphyrin skeletons have been well documented as playing important roles in relevant biological processes. In contrast, out-of-plane binding to the N-core of large metal cations as period 6 post-transition elements has remained poorly investigated. We describe herein monometallic complexes of Pb(II) and Bi(III) with 5,10 single strapped porphyrin ligands bearing a carboxylic acid group with two possible “in/out” orientations, in which the metal ions are bound to the N-core of the macrocycle either from the strap side or from the naked side. In the case of Pb(II), both the kinetics of insertion and resulting OOP stereoselectivity are influenced by the “in/out” stereoisomerism of the overhanging COOH. Remarkably, Bi(III) insertion proceeded quasi-instantaneously at RT owing to the transmetalation of its Pb(II) counterpart. The addition of a cyano group in position of the carboxylic acid group generates a ligand exhibiting an increased stereoselectivity in the metalation processes with Pb(II) and Bi(III): these cations are coordinated exclusively from the naked and strap side of the macrocycle, respectively. This difference in behavior is likely explained by steric hindrance for the divalent cation, which is counterbalanced by the establishment of the second sphere of coordination with the strap for the trivalent cation. Such a behavior is thought of interest for the further design of adaptable supramolecular coordination assemblies.

Pyrene-Functionalized Fluorescent Nanojars: Synthesis, Mass Spectrometric, and Photophysical Studies.

Nanojars are a class of supramolecular coordination complexes based on pyrazolate, Cu2+, and OH– ions that self-assemble around highly hydrophilic anions and serve as efficient anion binding and extraction agents. In this work, the synthesis, characterization, and photophysical properties of pyrene-functionalized fluorescent nanojars are presented. Three pyrene derivatives, 4-(pyren-1-yl)pyrazole (HL1), 4-(5-(pyren-1-yl)pent-4-yn-1-yl)pyrazole (HL2), and 4-(3-(pyrazol-4-yl)propyl)-1-(pyren-1-yl)-1,2,3-triazole (HL3), and the corresponding nanojars were synthesized and characterized using nuclear magnetic resonance spectroscopy and mass spectrometry. Electronic absorption, steady-state, and time-resolved fluorescence measurements were carried out to understand the interaction between the pyrene fluorophore and copper nanojars. Optical absorption measurements have shown minor ground state interaction between the fluorophore and nanojars. The fluorescence of pyrene is significantly quenched when attached to nanojars, suggesting strong contribution from the paramagnetic Cu2+ ions. Significant static quenching is observed in the case of L1, when pyrene is directly bound to the nanojar, whereas in the case of L2 and L3, when pyrene is attached to the nanojars using flexible tethers, both static and dynamic quenching are observed.

Metallacycle-crosslinked supramolecular polymers constructed by amino–YNE click reaction with enhanced mechanical properties

Supramolecular polymers based on supramolecular coordination complexes (SCCs) have received extensive attention because of their good stimulus responsiveness, processability and other properties. Herein, we report metallacycle-crosslinked supramolecular polymers via amino–yne click reaction, which were employed as well-performing elastomer materials. The supramolecular polymers cross-linked by the metallacycle not only maintained the aggregation induced emission (AIE) properties of the metallacycle, which were used to detect nitroaromatic explosives, but also had enhanced mechanical strength and toughness and exhibited elastomeric properties. This study provides a feasible strategy for the preparation of metallacycle-based supramolecular polymers with better mechanical properties.

A new nanosized host-guest supramolecular coordination polymer based on copper cyanide network and 1,7-diaminoheptane: Comparative structure study and catalytic activity

• A new 3D-host-guest supramolecular coordination polymer (SCP); ∞ 3 [(Cu 3 (CN) 3 ) 2 .(DAHP)], 1 had been synthesized by self-assembly at ambient conditions. • The [Cu 3 (CN) 3 ] 2 building blocks create unique complex structure containing the minicycle [Cu 2 (μ 3 -CN) 2 ] motif with wide cavities enable to capsulate the long chain DAHP as guest molecule. • The topology of 1 had been compared with the prototype SCP containing different aliphatic diamines. • The catalytic and photo-catalytic activity of 1 was studied for mineralization of methylene blue (MB) utilizing H 2 O 2 as an oxidant. New single crystals and the nanoscale particles of 3D-host-guest supramolecular coordination polymers (SCP 1 and 2 ); ∞ 3 [(Cu 3 (CN) 3 ) 2 .(DAHP)], [ 1,7-diaminoheptane=.(DAHP)] had been synthesized by self-assembly and utilizing ultrasonic radiation, respectively. X-ray single crystal diffraction of SCP 1 supported the formation of the [Cu 3 (CN) 3 ] 2 units exhibiting tetrahedral geometry of copper(I) atoms which had been assembled in unique way to construct 3D-network. The neutral [Cu 3 (CN) 3 ] 2 building blocks create pretty-complex structure containing the unique [Cu 2 (μ 3 -CN) 2 ] motif with wide cavities enable to capsulate the long chain DAHP as guest molecule. The topology and purity of 1 and 2 had been studied by elemental analysis, PXRD, IR-spectra, TEM and thermogravimetric analysis. The topology of 1 had been compared with the prototype SCPs containing different aliphatic diamines which indicated the effect of structural variability and flexibility of aliphatic diamines on the network structure of these SCP. The catalytic and photo-catalytic activity of the nanosized 2 was studied for mineralization of methylene blue (MB) utilizing H 2 O 2 as an oxidant.

Perylene Diimide-Based Multicomponent Metallacages as Photosensitizers for Visible Light-Driven Photocatalytic Oxidation Reaction

Perylene Diimide-Based Multicomponent Metallacages as Photosensitizers for Visible Light-Driven Photocatalytic Oxidation Reaction

Photocatalytic performance and mechanism of Rhodamine B with two new Zn(II)-based coordination polymers under UV-light

Two new supramolecular coordination polymers of [Zn(L)(bib)] (1) and [Zn(L)(phen)] (2) (H2L = 1,3-bis(3-carboxylphenoxy)benzene, phen = 1,10-phenanthroline and bib = 1,4-bis(1-imidazoly)benzene), were hydrothermally prepared and full characterized. 1 exhibits 6-connected net with hxl topology having Schläfli symbol of {36.46.53}, while 2 shows 1D chain built by ZnII centers and L2− linkers. 1 and 2 demonstrated effectively photocatalytic performance to the disintegration of dyes Rhodamine B (Rh B), methyl orange (MO) and methylene blue (MB). The plausible mechanism displayed by 1 for the catalytic degradation toward Rh B was proposed using the trapping method and LC-MS studies.

Perylene Bisimide-Cored Supramolecular Coordination Complexes: Interplay between Ensembles, Excited State Processes, and Aggregation Behaviors.

Manipulating the optical properties of fluorescent species is challenging owing to complicated and tedious synthetic works. Herein, the photophysical properties of perylene bisimide (PBI) were effectively tuned by varying the geometrical arrangement of PBI moieties within supramolecular coordination complexes (SCCs), where a PBI-based dicycle (2) and a trigonal prism (3) were generated via using a typical 90° Pt(II) reagent, cis-(PEt3 )2 Pt(OTf)2 -based coordination-driven self-assembly approach. The ligand, an ortho-tetrapyridiyl-PBI (1), exhibits a moderate fluorescence quantum yield (∼13 %) and efficient inter-system crossing (ISC). 2, however, is much more emissive with a fluorescence quantum yield of ∼41 %, and the relevant ISC process is significantly hindered. The fluorescence quantum yield of 3 is merely ∼6 % due to the observed symmetry-breaking charge separation (SB-CS), which turns to triplet state upon charge recombination. Interestingly, 3 could be fully transformed into 2 by simply adding a suitable amount of a 90° Pt(II)-based neutral triangle. Moreover, 2 tends to form discrete dimers both in crystal and solution states, but 3 does not show the property. Therefore, controlling geometrical arrangement of fluorophores through coordination-driven self-assembly could be taken as another effective way to tune their excited state relaxation pathways and construct high-performance optical molecular materials, which generally have to be prepared via organic synthesis.

Developing “Polymer‐in‐Salt” High Voltage Electrolyte Based on Composite Lithium Salts for Solid‐State Li Metal Batteries (Adv. Funct. Mater. 41/2021)

Solid Electrolytes To develop electrolytes for high energy density solid-state batteries, in article number 2103049, Fang Lian and co-workers propose a novel “polymer-in-salt” solid electrolyte (PISE) via supramolecular interaction and coordination between PME polymers and LiPVFM/LiTFSI composite Li salts. The PISE possesses superior lithium ion transference number, high ionic conductivity, excellent electrochemical stability as well as improved interfacial compatibility with electrodes, thus enabling excellent cycle performance of high voltage cathodes in solid-state batteries.

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO2 Sequestration by Selective Binding of Carbonate

Nanojars are a class of supramolecular anion-incarcerating coordination complexes that self-assemble from Cu2+ ions, pyrazole, and a strong base in the presence of highly hydrophilic anions. In this work, we show that if the strong base (e.g., NaOH or Bu4NOH) is replaced by a weak base such as a trialkylamine, capped nanojars of the formula [{Cu3(μ3-OH)(μ-pz)3L3}CO3⊂{Cu(μ-OH)(μ-pz)}n] (pz = pyrazolate anion; L = neutral donor molecule; n = 27-31) are obtained instead of the conventional nanojars. Yet, to obtain capped nanojars, the conjugate acid side product originating from the weak base must be separated by transferring it to water either by precipitation of the water-insoluble capped nanojars or by liquid-liquid extraction. Full characterization using electrospray ionization mass spectrometry, UV-vis and variable-temperature 1H NMR spectroscopy in solution, and single-crystal X-ray diffraction, elemental analysis, and solubility studies in the solid state reveals similarities as well as drastic differences between capped nanojars and nanojars lacking the [Cu3(μ3-OH)(μ-pz)3L3]2+ cap. Acid-base reactivity studies demonstrate that capped nanojars are intermediates in the pH-controlled assembly-disassembly of nanojars. During the self-assembly of capped nanojars, CO2 is selectively sequestered from air in the presence of other atmospheric gases and converted to carbonate, the binding of which is selective in the presence of NO3-, ClO4-, BF4-, Cl-, and Br- ions.

Multiemission tunability with ultralong and time–dependent room-temperature phosphorescence from isophthalic acid-decorated carbazole by coordination–induced crystallization

Two building blocks with triplet exciton generation of carbazole and isophthalic acid were integrated together to yield CzIP, and the strategy of coordination-induced crystallization was adopted, two supramolecular coordination frameworks 1 and 2 were synthesized with CzIP as ligand. Interestingly, several stacking types of CzIP molecules could be tuned and achieved, these compounds not only generate efficient fluorescence, but also exhibit the long room temperature phosphorescence (RTP), the afterglow lifetime is up to 0.76 s of compound 1 with phosphorescence quantum yield (9.5%). Significantly, compound 1 and 2 not only exhibit the single-phased white emission, but also present the time-dependent afterglow color, showing the greatly promising for anti-counterfeiting application. Experimental results and theoretical calculations reveal that the molecule stacking play a leading role in the optical properties and coordination bonds show the strong power to regulate the conformation and arrangement of organic molecules, and C–H···π bond can also play a significant role in the generation of long persistent phosphorescence. Importantly, integrating two phosphorescent chromophores with intermolecular charge transfer in a single–component organic molecular opens an efficient way to design the time-dependent room–temperature phosphorescence.

Mediated self-assembly of host-guest nano copper cyanide and 1,7-diaminoheptane: Design, catalytic and biological evaluation

Long chain aliphatic diamine, 1,7-diaminoheptane (DAHP), was selected as template for creation of novel nano-scaled 3D-guest-host- supramolecular coordination polymer (SCP); ∞3[(Cu3(CN)3)2.(DAHP)], 1. Crystal structure of SCP 1 consists of new bi-fold [Cu3(CN)3]2 fragments containing tetrahedral copper(I) atoms which are arranged in unique way to create 3D-structure exhibiting wide cavities enable to encapsulate the long chain DAHP as guest molecule. The topology of 1 had been elucidated by spectroscopic methods, elemental analysis, transmission electron microscopy (TEM) and scanning electron microscope (SEM). The nanosized SCP1 exhibits excellent catalytic activity towards mineralization of methyl violet (MV), methylene blue (MB) and indigo carmine (IC) dyes using H2O2 as oxidant within very short times. Scavenger techniques and disodium terephthalate (NaTA) as selective photoluminescence prob of hydroxyl radical had been utilized to elucidate mineralization mechanism. Nano-SCP 1 exhibits sigmoidal dose-response inhibition of cells viability giving low IC50 values for the tested cell as well as was examined for rate erythrocyte hemolysis and antioxidant activity utilizing ABTS assay. Also, SCP1 exhibits good antimicrobial activity due to the low MIC values keeping it a promising drug candidate for the treatment of the tested bacterial and fungal infections.

Coordination Polymers and Metal-Organic Frameworks: Structures and Applications—A Themed Issue in Honor of Professor Christoph Janiak on the Occasion of His 60th Birthday

This themed issue of Chemistry is in honor of Professor Christoph Janiak on the occasion of his 60th birthday, and celebrates his innovative contributions to the fields of supramolecular chemistry, coordination polymers, networks and metal-organic frameworks, inorganic/organic hybrid materials and inorganic materials from ionic liquids [...]

A Dynamic Chemical Clip in Supramolecular Framework for Sorting Alkylaromatic Isomers using Thermodynamic and Kinetic Preferences.

Adsorptive chemical separation is at the forefront of future technologies, for use in chemical and petrochemical industries. In this process, a porous adsorbent selectively allows a single component from a mixture of three or more chemical components to be adsorbed or permeate. To separate the unsorted chemicals, a different adsorbent is needed. A unique adsorbent which can recognize and separate each of the chemicals from a mixture of three or more components is the necessity for the next generation porous materials. In this regard, we demonstrate a "dynamic chemical clip" in a supramolecular framework capable of thermodynamic and kinetics-based chemical separation. The dynamic space, featuring a strong preference for aromatic guests through π-π and C-H⋅⋅⋅π interactions and adaptability, can recognize the individual chemical isomers from mixtures and separate those based on thermodynamic and kinetic factors. The liquid-phase selectivity and separation of the aromatic isomers are possible by the adaptability of the "chemical clip" and here we elucidate the prime factors in a combinatorial approach involving crystallographic evidence and detailed computational studies.

A 3D supramolecular Ag(I)-based coordination polymer as stable photocatalyst for dye degradation

Coordination polymers are multidimensional materials that can be utilized as photocatalytic materials for photodegradation of aromatic dyes. Herein, a new d10-configuration based Ag(I) supramolecular coordination polymer (CP) having formula {[Ag3(bib)2]·(H3L)2} (1) has been synthesized solvothermally using 1,3-bis(3,5-dicarboxylphenoxy)benzene (H4L) and 1,4-bis(1-imidazoly)benzene) (bib) ligands. The diimidazole ligand (bib) coordinates with Ag(I) where metal center adopts bi-coordinate linear-geometry to form cationic 1D coordinate chain, which is wrapped between 2D hydrogen-bonded organic plane to engender 3D suramolecular network. The CP is used as photocatalyst for the safe and sustainable decomposition of aromatic dyes. The percentage decomposition of dyes methylene orange (MO), Rhodamine B (Rh B), methylene blue (MB) and basic green (BG) are 5.44%, 61.38%, 63.75% and 83.31%, respectively under UV light irradiation. The plausible pathway using which the CP executed the decomposition of dyes proposed by theoretical calculations.

Coordination-driven hierarchically structured composites with N-CNTs-grafted graphene-confined ultra-small Co nanoparticles as effective oxygen electrocatalyst in rechargeable Zn-air battery

Rational design and fabrication of optimal reversible oxygen electrocatalysts are essential yet still remain great challenges for rechargeable metal-air batteries. Supramolecular coordination polymer-derived strategy for transition metal–nitrogen–doped carbon (M–N/C, M = Co, Fe, etc.) composites catalysts has been deemed promising in preserving rich M–Nx coordination modes and enhancing their intrinsic activities. However, the closely packed and nonporous characteristics of coordination polymer usually lead to the serious agglomeration of metallic nanoparticles and lack of porous channels after pyrolysis, impacting the abundance and accessibility of the exposed active sites during electrocatalysis. In this work, we put forward a new tactic to obtain ultra-small Co nanoparticles confined within N-doped carbon nanotubes grafted to reduced graphene oxide (Co/N-CNTs@rGO) through a coordination-driven in situ self-assembly approach followed by pyrolysis. The integration of high intrinsic activity, enhanced conductivity, populated and richly exposed active species throughout the laminated hierarchical composite structure endows Co/N-CNTs@rGO with appealing bifunctional oxygen electrocatalysis properties. Impressively, Co/N-CNTs@rGO was subsequently fabricated as the air electrode in a rechargeable Zn−air battery, and the device achieves a maximum power density of 168 mW cm−2, a large specific capacity of 765 mA h g−1 while maintaining satisfying cycling durability. This work may provide valuable insights in regulating the coordination polymer derivatives and bring new perspectives for future design of promising composites electrocatalysts for electrochemical conversions and energy storage technologies.

Chiral Coordination Metallacycles/Metallacages for Enantioselective Recognition and Separation

AbstractIn recent years, chiral discrete supramolecular coordination complexes have attracted increasing interest as simple enzyme mimetics owing to their aesthetic architectures and potential applications in chiral science. This review summarizes the recent advances on chiral coordination metallacycles/metallacages with inherent cavities for enantionselective recognition and separation, including their design principles and synthesis, the introduction of chirality and functionality, structural adaptability, and host‐guest bonding in enantioselective process. Finally, the perspectives on the remaining challenges and future opportunities are presented.

WCO biodiesel production by heterogeneous catalyst and using cadmium (II)-based supramolecular coordination polymer additives to improve diesel/biodiesel fueled engine performance and emissions

WCO biodiesel production by heterogeneous catalyst and using cadmium (II)-based supramolecular coordination polymer additives to improve diesel/biodiesel fueled engine performance and emissions