Supramolecular Coordination Polymers Research Articles

The impact of environmentally friendly supramolecular coordination polymers as carbon steel corrosion inhibitors in HCl solution: synthesis and characterization

Two 3D-supramolecular coordination polymers (SCP1 & SCP2) have been synthesized and characterized by physicochemical and spectroscopic methods. In a solution of 1.0 M HCl, SCPs were used to prevent corrosion of carbon steel (CS). The inhibition productivity (%η) rises as the synthetic inhibitor dose rises, and the opposite is true as the temperature rises. The study was carried out using chemical (mass loss, ML) and electrochemical ( potentiodynamic polarization, PDP and electrochemical impedance microscopy, EIS) techniques, which showed %η reached to 93.1% and 92.5% for SCP1 & SCP2, respectively at 21 × 10−6 M, 25 °C. For the polarization results, SCPs behave as mixed-type inhibitors. With increasing doses of SCPs, the charge transfer resistance grew and the double layer's capacitance lowered. The creation of a monolayer on the surface of CS was demonstrated by the finding that the adsorption of SCPs on its surface followed the Henry adsorption isotherm. The parameters of thermodynamics were computed and explained. The physical adsorption of SCPs on the surface of CS is shown by the lowering values of free energy (∆Goads < − 20 kJ mol−1) and increasing the activation energy (E*a) values in presence of SCP1 & SCP2 than in their absence. Atomic force microscope (AFM) and scanning electron microscopy (SEM) demonstrated the development of a protective thin film of SCPs precipitated on the surface of CS. There is a strong matching between results obtained from experimental and theoretical studies. Results from each approach that was used were consistent.

Fe doped Mo-Ni supramolecular coordination polymer based bifunctional oxygen electrocatalyst with high efficiency and duration for rechargeable zinc-air battery

In the present area of electrochemistry, due to the scarcity and unavailability of precious metals, it is a great challenge and a new opportunity to develop bifunctional electrocatalysts for zinc-air batteries (ZABs) with high activity, low cost and strong durability. In this study, an excellent electrocatalyst (Fe@MoNi/NCP-800) for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) was successfully prepared by pyrolyzing Fe2+ ion doped bimetallic Mo-Ni supramolecular coordination polymer (SCP) at 800 °C with carbon paper (CP) as self-supporting material. Owing to its unique FeNi alloy nanotube structure supported by the in situ formed MoN and the trimetallic synergies, the as-obtained electrocatalyst showed superior catalytic performance to that of commercial Pt/C half-wave potential (E1/2) of 0.846 V and RuO2 overpotential (η) of 300 mV. In addition, the ZABs prepared with Fe@MoNi/NCP-800 has a small charge–discharge voltage gap of 0.85 V, high energy efficiency of 35.25% and excellent cycle performance (308 h) at 10 mA cm−2. This research provides a very promising transition-metal alloy multifunctional electrocatalyst for the development of ZABs with high efficiency and duration, and a meaningful idea for the future rational design and synthesis of new coordination polymer or supramolecular coordination polymer-based electrocatalysts.

Two New Coordination Polymers Based on Viologen Ligands: Synthesis, Photochromism and Ammonia Sensing

Synthesized two supramolecular coordination polymers, {Cd3[(bcbpy)3Cl6]·8H2O}n (1) (bcbpy=1,1′-bis(3-carboxybenzyl)-4,4′-bipyridinium) and {Zn[(bcbpy)0.5(nip)]·H2O}n (2) (nip2-=5-nitroisophthalic acid anion), showed good photochromic properties when both coordination polymers changed from yellow to dark green under light stimulation, and the primary color could be restored at 85-95 ℃ for 60 min, this reversible cycle can be repeated more than 5 times. This photochromism is caused by photoinduced electron transfer to viologen free radicals. In addition, in ammonia vapor, both complexes changed from yellow to tan, showing good ammonia sensing characteristics. Research has found that complexes 1 and 2 exhibit sensing differences, with a response rate to light of 2>1. This sensing difference is mainly related to the D-A distance between molecules, π-π interactions, and the regulatory effect of metal ions or secondary ligands.

Coordination-driven stacking of carbazole-based molecule for dynamic long-lived room temperature phosphorescence

Distinguishing from static room temperature phosphorescence (RTP) materials, time-evolution dynamic RTP still face great challenges. In this work, we obtained two supramolecular coordination polymers [Cd2(CzIP)2(2-MIM)2] (1) and [Zn2(CzIP)4(DMI)2] (2) (CzIP ​= ​5-(carbazol-9-yl) isophthalate, 2-MIM ​= ​2-methylimidazole, DMI ​= ​N, N-Dimethylacetamide). These two compounds have the similar H-aggregation of carbazole fragments but with different overlap degree, but exhibit the different optical performance in phosphorescence lifetimes and stimuli responsive properties. The lifetimes of compounds 1 and 2 is 700.31 and 18.68 ​ms, respectively. Surprisingly, compound 1 exhibits dynamic room temperature phosphorescence with the color change from orange to green over the while delayed time. These results demonstrates that the coordination-tunable stacking behaviors play an important role in the generation of room temperature phosphorescence.

Emissive‐Dye/Cucurbit[n]uril‐Based Fluorescence Probes for Sensing Applications

AbstractSupramolecular host‐guest chemistry has provided many opportunities for the design and construction of new fluorescent systems in various applications, particularly in the field of sensing. Owing to the special structure and fascinating utilities, cucurbit[n]urils (CB[n]s) existing themselves as a young family of molecular vessels, it construction a stable host‐guest supramolecular complex with a variety of fluorescent dyes and indicators, that has been used as a powerful fluorescent probe and is widely used in sensing and related research fields. Therefore, in this review article, we will outline and attention on the recent advances in the progress of various CB[n] ⋅ guest‐based fluorescent probes, it can provide a general overview of the construction, detection mechanism and fluorescence sensing of certain metal ions, biomolecules and toxic chemicals. Examples of the selection of other types of CB[n]‐based supramolecular assemblies and coordination polymers will also be covered. Finally, we will also provide important views on fluorescent CB[n] ⋅ guest‐based inclusion complex for metal ion and biomolecular sensors.

Metalloporphyrins: their multitalented nature as observed in multi-metal complex systems.

Five topics pertaining to the unique chemistry of metalloporphyrins as observed in multi-metal complex systems are introduced. The topics include the following: (i) the unique chromatographic separation of cyclic porphyrins on modified silica gel; (ii) room temperature phosphorescence from the zinc porphyrin part in a zinc porphyrin/rhenium complex hetero dyad; (iii) the substituent effect, in the preparation of a readily soluble special-pair-type zinc porphyrin dimer/rhenium complex having efficient photocatalytic CO2 reduction ability; (iv) assessment of the excited triplet state of a special-pair-type zinc porphyrin dimer in macrocyclic multiporphyrin rings; and (v) solvation/desolvation indicators based on exclusive transformation between the head-head type and head-tail type of supramolecular co-ordination polymers composed of bis(zinc porphyrin)s.

A benzothiadiazole-based Pt(II) coordination polymer as an efficient heterogeneous photocatalyst for visible-light-driven aerobic oxidative coupling of amines.

An emissive Pt(II) coordination polymer (TBP) was synthesized by assembling a benzothiadiazole-based Pt(II) acceptor (A) with a tetraphenylethene (TPE) containing donor (L). Multiple benzothiadiazole units in the polymeric array of the TBP rendered it with reactive oxygen species generation ability. TBP was found to be an excellent photocatalyst for oxidative coupling of benzylamine under visible light with full conversion within 2 hours at room temperature and reusability for multiple cycles. Such photocatalytic efficiency under ambient conditions, reusability of the catalyst, and easy separation of the product are noteworthy.

Controllable preparation of supramolecular coordination polymers based on carboxylated pillar[n]arenes and zinc ions: An efficient tool for paraquat removal from water

Supramolecular coordination polymers Zn2+@WP5 and Zn2+@WP6 have been designed and controllable prepared through coordination interaction between pillar[n]arenes (carboxylated pillar[5]arenes (WP5) and carboxylated pillar[6]arenes (WP6)) and zinc ions. Taking advantages of the host–guest interaction between pillar[n]arenes and paraquat (PQ), Zn2+@WP5 and Zn2+@WP6 can adsorb PQ efficiently. In particular, in comparison with Zn2+@WP6, Zn2+@WP5 can achieve the separation of PQ efficiently, mainly benefiting from its high surface area. The adsorption ability of Zn2+@WP5 was explored systematically including adsorption kinetics, thermodynamic adsorption analysis as well as the influence of pH and ionic strength. The maximum adsorption capacity of PQ was about 203.60 mg/g. In addition, Zn2+@WP5 could be regenerated and efficiently adsorb PQ in tap and river water sample. This work extends the application of pillar[n]arenes-based supramolecular coordination polymers in micro-pollutants separation and removal.

Ultrasound‐driven design and catalytic activity of nanostructured Cobalt (II) 3D‐supramolecular coordination polymer

Nanosized photo-catalysts are an intriguing study topic for achieving high catalytic performance. The self-assembly reaction and ultrasonication-induced self-assembly of, cobalt nitrate hexahydrates, ethyl isonicotinate (EIN) and SCN anion as connecting ligand, resulted in the crystalline supramolecular coordination polymer, SCP1; [Co(EIN)4(SCN)2], and the nanoparticles SCP1\\, [Co (EIN)4 (SCN)2], respectively. X-ray diffraction of single crystals SCP1 indicated octahedral geometry of CoII. SCP1's network structure is made up of [Co(EIN)4 (SCN)2] fragments linked via extended hydrogen bonds, creating 1D-chains. The production of H-bonds, which extend the structure to a 3D-network, is dependent on the free ethyl carboxylate groups. SCP1 and SCP1\\ were characterized with different structural characterization techniques and spectral studies. The catalytic evaluations of SCP1 and SCP1\\ as heterogeneous catalysts bolster exceptionally effective catalytic action towards the corruption of indigo carmine color (IC) as a targeted pollutant in exceptionally brief times beneath UV-radiation or ultrasonic waves. To detect the reactive oxygen species and reaction mechanism, photoluminescence probing technology was applied using the disodium salt of terephthalic acid.

Synthesis, characterization and antimicrobial property in vitro of supramolecular coordination polymers bearing brominated Schiff base ligand

In this study, two supramolecular coordination polymers of Co(II) and Zn(II) based on brominated Schiff base (E)-4-bromo-2-((quinolin-6-ylimino)methyl)phenol (HL) were synthesized and characterized by using elemental analysis, IR spectroscopy and NMR spectroscopy. Furthermore, the crystal structures of HL, CoL2 (І) and ZnL2 (II) were determined by single crystal X-ray analysis. It was revealed that the bromine-related interaction played important role in the self-assembly of HL supramolecular network. The crystal structural investigations revealed that І and II were isomorphous with the same geometry around the metal atom and similar structural feature. The stable four-membered chelate structure resulted from coordination between the metal(II) ion and deprotonated bidentate ligand. And supramolecular coordination polymers of І and II formed diverse architecture through multiple hydrogen bondings, π···π interactions and halogen-related interactions. Antimicrobial activities of polymers were tested toward four bacteria and five phytopathogenic fungi. І and II showed higher activities toward the tested microorganisms than HL. Furthermore, the photoluminescence results indicated that HL and II accompanied with better fluorescence properties in the ultraviolet region.

Highly efficient bifunctional catalyst with 2D MoN formed in situ synergy for OER and ORR based-on Co(II) doped Mo(IV)-Ni(II) supramolecular coordination polymer

Developing non-precious metal oxygen electrocatalysts is of great significance for storage systems and energy conversion. Pyrolyzation of the bimetallic Mo(IV)-Ni(II) supramolecular coordination polymer (SCP) for the first time by simultaneously introducing Co(II) ion with Graphene Oxide (GO) as template leads to a new outstanding oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional electrocatalyst (GO-Co@MoNi) composed structurally by 2D MoN flake formed in situ and CoNi alloy supported on lamellar GO. The unique components, sheet architecture, and intermetallic synergy of the GO-Co@MoNi catalyst (η = 340 mV, E1/2 = 0.855V) endow it comparable electrocatalytic performance towards OER to the commercial RuO2 electrocatalysts (η = 320 mV) and superior performance towards ORR to Pt/C (E1/2 = 0.84 V) electrocatalyst. Density functional theory (DFT) calculation reveals the essential role of trimetallic synergy at an unprecedented “comfortable” 4 × 1e− electrons reaction pathway in the excellent ORR in GO-Co@MoNi. The current research opens a skillful design strategy and a rare catalytic mechanism for constructing new oxygen electrocatalysts, and the results show that the SCP-based materials have great potential in the electrochemical field in the future, especially for efficient bifunctional electrocatalysts.

Ultrasonic assisted structures and biological characteristics of nanoscale silver coordination polymers with cyanide, azide and 4,4\\-bipyridine ligands

Ultrasonic self-assembly method was utilized to prepare new nano supramolecular coordination polymers (SCPs), 3∞[AgN3(bpy)], NSCP1 and 3∞[(AgCN)2 (bpy)], NSCP2 [bpy= 4,4\\-bipyridine] while the single crystals were prepared at ambient conditions. The silver atom in 1 acquires square planer geometry via coordination to four nitrogen atoms while NSCP2 contains two crystallographically different silver atoms adopting distorted trigonal planar geometry. The structures extend via corrugated catenated (AgN3) or (AgCN) chains which are linked by bpy forming 2D-layer structure. The 2D-layers are interconnected by π–π stacking, H- bonds and argentophilic interactions creating 3D-network structure. TEM images support nanoscale particles of NSCPs1 and 2. NSCPs 1 and 2 had been utilized as potent anticancer and anti-pathogenic micro-organisms. In vitro cytotoxicity and cell viable activity of the NSCPs1 and 2 had been studied against a set of different human cancer cell lines. The higher level of the NSCPs cytotoxicity was recorded against MCF-7 and HePG2 cells. Also, they own a good ability to inhibit the growth of the tested neoplastic cells and a poor effect on the normal cells in comparison with the results of cisplatin. Also, antioxidant activities, erythrocyte hemolysis, DNA binding and antimicrobial activities had been investigated.

New Cu(II)-based three dimensional supramolecular coordination polymer as photocatalyst for the degradation of methylene blue

A new Cu(II)-based coordination polymer [Cu2(HL)2(bib)2] (1) has been synthesized by reacting two flexible linkers viz. 5-(4ˊ-carboxylphenoxy)isophthalic acid (H3L) and 1,1′-(1,4-butanediyl)bis(imidazole) (bib) a N-donor auxiliary ligand with CuSO4 under solvothermal condition. The single crystal X-ray analysis indicates that 1 possess 2D layered network, which further extends into 3D supramolecular framework through hydrogen bonding interactions. The coordination polymer 1 has been used as photocatalyst for the sustainable degradation of model aromatic dyes viz. methylene blue (MB), Rhodamine B (Rh B) and methylene orange (MO). The experiments demonstrate that 1 exhibits recyclable and better photocatalytic activity for photodegradation of MB (62.96%) than Rhodamine B (Rh B) and methylene orange (MO) in time span of 100 min. Furthermore, trapping experiments using scavengers indicate that hydroxyl radicals are the main species responsible for photocatalytic degradation of MB. Apart from this computational investigation has been executed to propose the plausible mechanism of photocatalysis.

Supramolecular chain-like polymers based on Ln(III) aqua complexes and cucurbit[6]uril

Five new supramolecular coordination polymers based on cucurbit[6]uril (CB[6]) and mononuclear lanthanide (III) ions were synthesized and structurally characterized by single-crystal X-ray diffraction. They are [{Nd(H2O)5(NO3)}2(CB[6])](NO3)4·7H2O (1), [Gd(H2O)3(dmf)(CB[6])(NO3)](NO3)2·5H2O (2), [Gd(H2O)4(CB[6])(NO3)](NO3)2·7H2O (3), [Gd(H2O)3(dmf)(CB[6])(HCOO)](NO3)2·6H2O (4), and [{Ho(H2O)6}2(CB[6])]Cl6·6H2O (5). The crystal structures of complexes 1–5 showed that packing of mononuclear ions and macrocycles gives rise to supramolecular chain-like polymers. The complexes were characterized by TG, elemental analysis, and IR spectroscopy. The fluorescent properties for 1, 3 and 5 were analyzed. The magnetic properties of 2 and 4 were also studied.

Ultrasound-assisted synthesis and biological activity of nanosized supramolecular coordination polymers of silver(I) with chloride, thiocyanate, and 4,4′-bipyridine ligands

Nanosized crystals of coordination polymers (SCPs) [AgCl(bpy)2] (1) (bpy = 4,4′-bipyridine) and [AgSCN(bpy)0,5] (2) were prepared by precipitation method with ultrasonication. The silver atom acquires trigonal bipyramidal topology via coordination to 3 chloride atoms and 2 nitrogen atoms of 2 bpy ligands forming two fused 4-cycles [Ag2Cl2] for SCP1. Compound 1 is a 2D coordination polymer consisting of 1D ribbons [Ag2Cl2] interconnected by bpy linkers on both sides of the layer. The structure of SCP1 extends to 3D via the formation of successive 2D-layers connected by van der Waals interactions. The coordination polymer 2 has the 3D structure consisting of parallel 2D layers [Ag(SCN)2] interconnected by bpy linkers into the framework. The structure of 2 is further stabilized by argentophilic interactions. TEM shows nano sizes of the particles of 1 and 2. Cytotoxicity and cell viable activity of the nanosized 1 and 2 were investigated in vitro against a set of different human cancer cell lines. DNA binding ability of 1 and 2 was done by Methyl green displacement. ABTS inhibition and hemolysis activity experiments were used for checking Antioxidant activity of 1 and 2. Antimicrobial activity of the nanosized 1 and 2 was carried out against some bacterial strains.

Rational Polyelectrolyte Design Enables Multifunctional Polyion Complex Vesicles.

Polyion complex (PIC) vesicles prepared by polyelectrolyte assembly have attracted extensive attention as distinctive carriers and nanoreactors, particularly for biological cargoes. However, the constrained regulation of their structure and functionality at this stage hinder the application of PIC vesicles. Herein, we design a new asymmetric assembly system, namely cationic-neutral-cationic triblock copolymer co-assembly with a supramolecular ionic coordination polymer. The former creates poly(ethylene oxide) (PEO) loops upon complexation, which are favorable for vesicle fabrication, while the coordination polyelectrolyte composed of metal ions and a dipicolinic acid (DPA)-based bis-ligand features well-defined functionalities depending on the incorporated metal ions. Thus, the rational combination allows controlled fabrication of PIC vesicles with a modulated structure and functionalities. Moreover, the encapsulation and release of hydrophilic dextran based on different PIC vesicles has been realized. Our design integrates the advantages of both triblock and coordination polymers, and therefore demonstrates a novel strategy for harmonious regulation of the structure and functionality of PIC vesicles. The revealed findings and achieved properties shall be inspirational for developing functional PIC vesicles and boosting their applications towards demand encapsulation and delivery.

Realization of Single-Phase White-Light-Emitting Materials with Time-Evolution Ultralong Room-Temperature Phosphorescence by Coordination Assemblies.

Two Cd-based supramolecular coordination polymers, [Cd3(CzIP)3(DMF)2] (1) and [Cd2(CzIP)2(DMF)4] (2), were synthesized by using 5-(carbazol-9-yl) isophthalate (CzIP) as ligands. These two compounds exhibit multiple luminescence emissions; apart from fluorescence, time- and temperature-dependent ultralong phosphorescence (RTP) were also achieved under room conditions. Significantly, compound 1 has a long-lived afterglow of 0.93 s at 545 nm under ambient conditions. Compound 2 shows nearly pure white-light emission with CIE coordinates of (0.33, 0.33) via the dual emission of fluorescence and phosphorescence. It has come to our attention that it is the first example of a luminescent coordination polymer with single-phase white-light emission and color-evolution RTP. In addition, the long-lived RTP materials can be used in time-dependent anticounterfeiting and white-light-emitting diodes. Experimental and singlet and triplet state calculations indicate that both C-H···π interaction and inter- and intramolecular charge transfer interactions could be beneficial to the emission of ultralong RTP.

Crystal engineering of aurophilic supramolecular architectures and coordination polymers based on butterfly-like copper–dicyanoaurate complexes: vapochromism, P–T behaviour and multi-metallic cocrystal formation

A family of bimetallic complexes based on aurophilic interactions was synthesized, and tested for vapochromism and P–T variations. These complexes can originate cocrystals, opening the route to a new aurophilic-based crystal engineering.

Synthesis, Characterization and Antimicrobial Property in Vitro of Supramolecular Coordination Polymers Bearing Brominated Schiff Base Ligand

Synthesis, Characterization and Antimicrobial Property in Vitro of Supramolecular Coordination Polymers Bearing Brominated Schiff Base Ligand

Design of coordination polymers based on combinations of 1,2-diphenylethane-1,2-diyl diisonicotinate with Cu(ii), Zn(ii), Cd(ii) and Co(ii)

Five new supramolecular coordination polymers of different dimensionalities (L-Cu(acac)2, L-Cu(hfac)2, L-ZnCl2, L-CdI2 and L-CoCl2) based on the use of the flexible organic ligand L (1,2-diphenylethane-1,2-diyl diisonicotinate) are reported.