Luminescent Coordination Polymers Research Articles

Multiresponsive luminescent Cd(II) coordination polymer for selective and recyclable detection of TNP and Cr2O72- in aqueous media

We report the solvothermal synthesis and fluorescent property of a novel luminescent coordination polymer (LCP) by choosing a new coplanar ligand, 2-(4-(3,5-dicarboxylphenoxy)phenyl) benzimidazole-5-carboylic acid (L). Single-crystal X-ray diffraction analysis reveals that the obtained LCP is formulated as {Cd(L2}n (1) and features a 2D uninodal 4-connected sql/Shubnikov tetragonal plane net with {44.62} topology. Fluorescence experiments suggest that 1 could work as highly sensitive and selective probe for both Cr2O72– and 2,4,6-trinitrophenol in water medium, resisting interferences from a variety of competitive anions or nitroaromatic compounds. The limits of detection for Cr2O72– and TNP in aqueous solutions were calculated to be 0.128 and 0.089 μM, respectively. Just by a simple method, the fluorescent sensing ability of 1 could be regenerated.

A New Preorganized Metalloligand Linker for the Construction of Luminescent Coordination Polymers

A series of heterometallic coordination polymers, [[La(UO2)(bptc)(H2O)8][(UO2)(Hbptc)]·6H2O]n (1), [Cd(UO2)3(bptc)2(H2O)2]n (2), [Zn(UO2)3(bptc)2(H2O)2]n (3), and [Mn(UO2)(bptc)(H2O)3]n (4) (H4bptc...

TWO 3D Cd (II) luminescent coordination polymers as highly selective and sensitive sensing for Fe3+ and CrO42−/Cr2O72− ions in aqueous system

Two 3D Cd (II) luminescent coordination polymers (LCPs), namely, {[Cd(bimb)Cl2]·1.5H2O}n (1) and {[Cd1.5(bbib)2.5Cl2]·3H2O·NO3}n (2) { bimb ​= ​1,3-Bis (imidazol-1-ylmethyl) benzene, bbib ​= ​1,4-bis (benzoimidazo-1-ly) benzene } have been obtained under solvothermal conditions The structural analysis of LCPs exhibited that they are 3D frameworks with (4,6)-connected dia network for 1 and (4,5)-connected tck topology network for 2. The solid state fluorescence of ligands and LCPs, and luminescent sensing experiments of LCPs for anions and cations in aqueous solutions were systematically studied. Compared with the free bimb and bbib ligands, the emission peaks of 1 and 2 are slightly red-shifted, which can be assigned to the effect of coordination. Furthermore, the fluorescence experiments indicated that LCPs 1 and 2 have high sensing sensitivity and selectivity toward Fe3+ and CrO42−/Cr2O72− ions in water system.

A water-stable luminescent coordination polymer for sensitive detection of nitroaromatic compounds

A two-dimensional (2D) interwoven coordination polymer, Cd-TTPBA-4 ([Cd(TTPBA-4)2(OH)2·H2O]n, TTPBA-4 = N,N,N’,N’-tetrakis(4-(4H-1,2,4-triazol-4-yl)phenyl)benzene-1,4-diamine), was constructed using π-electron rich conjugated 4-substituted-1,2,4-triazole based ligands. The structure had a warp-and-woof interwoven framework which was composed of ribbon-like one-dimensional (1D) chains through π − π stacking interactions. The Cd-TTPBA-4 sample was further characterized in detail by powder X-ray diffraction, FT-IR, thermogravimetric analysis, and N2 adsorption. The fluorescence sensing measurements demonstrated that Cd-TTPBA-4 as a sensitive sensor for the detection of various nitroaromatic compounds had a low limit of determination. The corresponding Ksv value of 2,4,6-trinitrophenol (TNP), 2,4-dinitrophenol (2,4-DNP) and p-nitrosophenol (PNP) were accurately calculated about 4.7 × 104 M−1, 4.1 × 104 M−1, and 2.2 × 104 M−1, respectively. Cd-TTPBA-4 also exhibited good stability and recyclability for five cycles.

A New Luminescent Zn(II) Complex: Selective Sensing of Cr2O72- and Prevention Activity Against Orthodontic Root Absorption by Suppressing Inflammatory Response.

A novel luminescent coordination polymer (CP) based on Zn(II) ions as nodes [Zn(OPY)1.5(Hbtc)]n (1), [H3btc = trimesic acid and OPY = 4,4'-(oxybis(4,1-phenylene))dipyridine] has been prepared via the solvothermal assembly of a tripodal multicarboxylic acid ligand, a bis-pyridyl ligand with V-shape containing two diverse coordination patterns as well as Zn2 + ion. The experiments of photoluminescence also reflect that the coordination polymer 1 has high sensitivity to potassium dichromate, and its quenching efficiency is Ksv of 2.12 × 104L·mol- 1. Furthermore, its treatment activity on orthodontic root absorption was evaluated in vivo. Firstly, the CCK-8 assay was performed in this research to evaluate the biotoxicity of the synthetic compound. Next, the TNF-α and Cbfα1 released by the periodontal ligament fibroblast was determined via the ELISA test kit. In addition to this, the signaling pathway of NF-κB activation after treated with compound was measured by the RT-PCR.

High Luminance of Heterolanthanide-Based Molecular Alloys by Phase-Induction Strategy

Reactions in water of lanthanide chlorides with the sodium salt of 4,5-dichlorophthalate (dcpa2-) lead to two families of isostructural coordination polymers: family F1 that gathers compounds with the general chemical formula [Ln2(dcpa)3(H2O)]∞ with Ln = La-Gd (except Pm) and family F2 that gathers compounds with general chemical formula [Ln2(dcpa)3(H2O)5·3H2O]∞ with Ln = Tb-Lu plus Y. Heterolanthanide molecular alloys that contain both Eu3+ and Tb3+ ions have been prepared in both structural families. Their luminescence properties have been studied, especially from the brightness point of view. This study revealed that structural family F1 provides molecular alloys that are much more luminescent than those of structural family F2. Therefore, a phase-induction strategy was followed that allowed the design of some molecular alloys (La/Tb/Eu and La/Dy) that are, to the best of our knowledge, among the most luminescent coordination polymers reported so far. This study opens the way to bright luminescent bar codes as well as to bright white luminescent lanthanide-based coordination polymers.

A novel microporous metal–organic framework for highly sensitive and selective photochemical determination of chlorpyrifos

A new trinuclear porous luminescent coordination polymer with 3,4,6-connected, {[Zn3(Hdpa)(OH)(H2O)2]·6H2O}n (1) (H6dpa = 3, 4-di(3,5-dicarboxyphenyl)phthalic acid), has been synthesized and characterized. Compound 1 contains one unprotonated carboxyl group that can function as a potential active site. Moreover, Luminescent investigations show that 1 exhibits highly effective and selective luminescent sensing for pesticide chlorpyrifos in aqueous solution, which makes its good candidates as luminescent sensors.

A highly selective and sensitive bifunctional luminescent sensor for TNP and Iron ion based on magnesium coordination polymer

A luminescent coordination polymer [Mg3L2(H2O)6]2·12H2O (1) (H4L+Cl-= 1,3-bis(3,5-dicarboxyphenyl)imidazolium) was synthesized and systematically characterized. Complex 1 is a 0D unit constructed by L3-, water and magnesium ions, which was further assembled into 0D → 2D → 3D network constructed via various H-bondings from free/coordinated water and π···π interactions. The fluorescence intensity of complex 1 has good stabilities in acid/base conditions, photoluminescence experiments show that complex 1 has high selectivity and sensitivity for sensing nitro compounds (NCs) and metal ions by luminescence quenching effect, especially for picric acid (TNP) and Fe3+ ions, the Ksv are up to 2.6 × 104 M−1 and 5.0 × 104 M−1. Further more, their possible quenching mechanisms have been studied separately.

Two Zn(II)-based coordination polymers: luminescent property and protective activity on optic neuritis by regulating MAPK-AKT signaling pathway

In the current study, two new luminescent coordination polymers based on Zn(II) ions as nodes, {[Zn3(tcpb)2(bibp)2]·4dioxane·DMF·H2O}n (bibp = 4,4′-bis(imidazol-1-yl)biphenyl) and {[Zn(Htcpb)(4,4′-bpy)·(DMF)·(dioxane)0.5·(H2O)2]}n (4,4′-bpy = 4,4-bipyridine), were prepared from polycarboxylate ligand 1,3,5-tris(4-carbonylphenyloxy)benzene (H3tcpb) as well as different N-donor co-ligands. In addition, the luminescent sensing performance for {[Zn3(tcpb)2(bibp)2]·4dioxane·DMF·H2O}n was explored, which shows that it could behave as the sensor of acetylacetone (acac) containing high sensitivity and selectivity. Furthermore, the treatment effect of the compounds on optic neuritis was evaluated. Firstly, the relative expression of the inflammatory genes mapk and akt was measured by RT-PCR. Besides, the release for the TNF-α and IL-1β into plasma was measured by ELISA detection kit.

Koordinazio-polimero luminiszenteak: gailu argitsuen etorkizuna

Koordinazio-polimero luminiszenteak aurreko mendetik ezagutzen diren arren, izugarrizko hazkundea izan dute aurreko hamarkadatik gaur egun arte, erakusten duten argi-igorpen gaitasun paregabeei esker. Material horiekin, gailu argitsuen arloan belaunaldi berri bat garatzen hasi da, bereziki sentsore gisa edo faltsifikazio-sistemetan erabiltzeko. Material hauen aplikazio gehienek intentsitate handiko igorpenak edota igorpen iraunkorrak izatera behartzen dute. Zentzu horretan, koordinazio-polimeroak aukera egokiak dira, beren izaera metal-organikoa dela eta; haien egitura kristalinoa nahi diren propietate fotoluminiszenteak erakusteko diseina daitezke, horrela eginkizun zehatz batera bideratzeko. Azpimarratzekoa da azken urteotan ikusi egin dela koordinazio-polimeroek iraupen luzeko argi-igorpenak emateko gaitasuna daukatela. Lan honen helburu nagusia da koordinazio-polimero luminiszenteak eta, bereziki, argi-igorpen fosforeszenteak sortzen dituztenak nola eraiki eta haietan gertatzen diren fenomenoak azaltzea.

Luminescent Coordination Polymer for Picric Acid Detection and Treatment on Spinal Cord Injury Model Via Upregulating the trka Expression.

A luminescent coordination polymer based on Tb(III) has been synthesized with the tripodal carboxylic acid ligand containing N,O codonors (H2PBA = 5-[4-pyridin-3-yl-benzoylamino]-isophthalic acid) as ligand under solvothermal conditions. The chemical formula of this polymer is {[Tb2(PBA)3(H2O)3]·DMF·3H2O}n (1). Complex 1 has good sensitivity and selectivity to picric acid (PA). At 0-30μmol/L, 1's quenching constant is 4.5 × 104L/mol. In the biological function study, the motor function of spinal cord-injured animals after different treatments was evaluated using the blood-brain barrier (BBB) method. The trka expression level on the neural stem cells after treatment was measured to reveal the underlying mechanism.

Microwave and conventional synthesis, characterization, photophysical properties, toxicity and bacterial staining of new mesoporous zinc(II)-based luminescent coordination polymer

In this paper we reported the microwave assisted and conventional syntheses of new mesoporous zinc-based luminescent coordination polymer (2: catena-poly[(aquazinc-μ-5-ylmethyleneamino-8-quinolinolate-O:N)-μ-(benzoate-O:O)]) derivative from new rigid Schiff base linker (1a: (E)-4-((quinolin-5-ylmethylene)amino)benzoic acid). The microwave-assisted synthesis allows getting aggregates of nanoparticles with high crystallinity in good yields, which demonstrated to be a better synthetic route than conventional synthesis in terms of processing facility, short reaction time, and reproducibility. Mesoporous zinc-based luminescent coordination polymer 2 and its free Schiff base linker 1a were fully characterized by Raman, IR-ATR, EDX-FESEM, XRD and XPS techniques. In addition, free Schiff base linker 1a was also characterized by NMR (1H and 13C). The photophysical properties were analyzed in MeOH by UV–Vis and fluorescence spectroscopy revealing that both materials can be classified as semiconductor with fluorescence quantum yield in the 0.13–0.50 range. X-ray diffraction pattern of mesoporous zinc-based luminescent coordination polymer 2 synthetized under microwave irradiation exhibited high crystallinity and thermal analysis indicated that the nanostructures show one molecule of occluded into the polymer layers. The bacterial toxicity and staining studies by epifluorescence microscopy were carried out with the newly synthetized molecules. To the best of our knowledge, this is the first report of new mesoporous zinc(II)−based luminescent coordination polymer with a rigid Schiff base linker as spacer group and applied as bacterial-staining fluorescent probe.

Luminescent Coordination Polymers Constructed from a Flexible, Tetradentate Diisopyrazole Ligand and Copper(I) Halides.

One- and two-dimensional coordination polymers composed of a structurally flexible, tetradentate diisopyrazole ligand and copper(I) halides were synthesized as crystalline solids. Complexation with copper(I) chloride or bromide resulted in the formation of infinite coordination chains through connecting each diisopyrazole ligand with two copper(I) ions in a trigonal planar coordination geometry. Contrarily, the combination of a diisopyrazole ligand and copper(I) iodide gave a two-dimensional coordination network comprising Cu4 I4 units with stair-step type geometry and diisopyrazoles that acted as both tetradentate and bidentate bridging ligands. All the coordination polymers exhibited visible photo-emission upon UV irradiation, and the Cu4 I4 complex showed thermochromic behavior.

Front Cover: Luminescent Coordination Polymers Constructed from a Flexible, Tetradentate Diisopyrazole Ligand and Copper(I) Halides (Chem. Asian J. 5/2020)

An ethylene-bridged diisopyrazole ligand forms one- and two-dimensional luminescent coordination polymers through complexation with Cu(I) halides. While chloride and bromide form infinite coordination chains with trigonal planar copper(I) coordination geometry, iodide results in the formation of a coordination network with stair-step type Cu4I4 subunits that exhibits thermochromic emission. These results illustrate the inherent structural flexibility of the diisopyrazole ligand to adopt both planar and stepped conformations in the solid state. More information can be found in the Full Paper by Yasuhide Inokuma et al. on page 601 in Issue 5, 2020 (DOI: 10.1002/asia.201901682).

A pH-stable Ag(i) multifunctional luminescent sensor for the efficient detection of organic solvents, organochlorine pesticides and heavy metal ions.

Developing novel luminescent materials for sensitive and rapid detection of heavy metal ions, organic solvents and organochlorine pesticides is vital for environmental monitoring. Herein, a new Ag(i) luminescent coordination polymer [Ag(3-dpyb)(H3odpa)]·H2O (LCP 1) (3-dpyb = N,N′-bis(3-pyridinecarboxamide)-1,4-butane, H4odpa = 4,4′-oxydiphthalic acid) was obtained by a hydrothermal reaction and characterized by single crystal, powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and luminescence spectroscopy. LCP 1 is a three-dimensional (3D) supramolecular framework formed from 1D [Ag-3-dpyb-H3odpa]n chains and H-bond interactions. The luminescence sensing study of LCP 1 for recognizing organic solvents, organochlorine pesticides and heavy metal ions was performed, which demonstrated it to be a potential luminescent sensor for Hacac, NB, 2,6-DCN, Fe2+, Hg2+, and Fe3+. Fe2+, Hg2+, and Fe3+ in river water were determined using LCP 1 with satisfying recovery.

Multi-responsive chemosensing and photocatalytic properties of three luminescent coordination polymers derived from a bifunctional 1,1′-di(4-carbonylphenyl)-2,2′-biimidazoline ligand

Three 3D ZnII/CdII CPs were synthesized to act as multiresponsive luminescent sensors for Fe3+, Cr2O72− and NZF antibiotic. The photocatalytic studies indicate that the CPs 1–3 have good photocatalytic capability in degradation of MB.

Three pairs of luminescent coordination polymers based on CoII and CdII clusters for the detection of antibiotics, pesticides and chiral nitro aromatic compounds.

Three couples of coordination polymers (CPs), namely, [Co((R/S)-Hcna)2]n (1-D/L), [Cd6((1R,2R/1S,2S)-cpba)4(phen)6(H2O)3]n (2-D/L) and [Cd2((1R,2R/1S,2S)-Hcpba)2(phen)2]n (3-D/L) {(R/S)-H2cna = (R/S)-6-(1-carboxyethoxy)-2-naphthoic acid, (1R,2R/1S,2S)-H3cpba = (1R,2R/1S,2S)-2,2′-((5-carboxy-1,3-phenylene)bis(oxy))dipropionic acid, phen = 1,10-phenanthroline} are successfully synthesized under hydrothermal conditions. Structural analysis shows that CP 1 has a 3D 3,6-c net structure with a point symbol of (4·62)2(42·610·83). CPs 2 and 3 are obtained under very similar reaction conditions except using different solvent ratios. The presence of the planar chelating ligand phen in CPs 2 and 3 limited the spatial growth of the structure, resulting in the formation of different 1D structures. All CPs crystallized in the chiral space group P21, CPs 1–3 are all SHG active. Their luminescence sensing activities for organics such as antibiotics, pesticides and nitro aromatics are also investigated. The results showed that CP 1 can effectively identify trace amounts of nitrofurans (NFs) and CP 3 has obvious recognition ability toward nitrofurans (NFs) and nitroimidazoles (NMs). Both CPs 1 and 3 could selectively detect 2,6-dichloro-4-nitroaniline (DCN). The luminescence of CPs 1 and 3 can also be quenched by (D/L)-4-nitrophenylalanine ((D/L)-NPA) and (1R,2R/1S,2S)-2-amino-1-(4-nitrophenyl)propane-1,3-diol ((1R,2R/1S,2S)-ANPO).

Construction of luminescent coordination polymers based on 5-(1-(carboxymethyl)-pyrazol-3-yl)isophthalic ligand for sensing Cu2+ and acetone

Two new coordination polymers (CPs), namely, [Zn3(L)2(phen)3(H2O)2·2H2O]n (phen = 1,10-phenanthroline) (1) and [Pb(HL)]n(2) were constructed from the coordination reaction of 5-(1-(carboxymethyl)-pyrazol-3-yl)isophthalic acid (H3L) ligand and Zn(II) or Pb(II) ions under hydrothermal conditions. It was found that 1 and 2 exhibited an infinite one-dimensional (1D) chain and three-dimensional (3D) framework with left-handed and right-handed helical chains based on single crystal X-ray diffraction analysis, respectively. Both of them had good luminescent property at room temperature. Meanwhile, 1 possessed highly luminescent sensing properties for environmentally relevant Cu2+ ions with a quenching coefficient Ksv of 1.509 × 104 M−1, and the fluorescence quenching efficiency of acetone reached 90%, which indicated that 1 could be taken as a potential candidate for developing multifunctional luminescent sensors. Our work thus paves a way for developing CPs as an appealing platform to construct crystalline materials for environmental applications.

Synthesis of two isostructural Zn-CPs and their fluorescence sensing for Cr (VI) ion and nitrofurantoin in aqueous medium

Two isostructural Zn (II) luminescent coordination polymers (CPs), namely, [Zn(tptc)0.5(bpy)]n (1) and [Zn(tptc)0.5(pyp)]n (2) {H4tptc ​= ​p-terphenyl-2,2″,5″,5‴-tetracarboxylic acid, bpy ​= ​2,2′-bipyridine, pyp ​= ​3-(pyrid-2-yl) pyrazole} were synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, Infrared spectra, powder X-ray diffraction, thermogravimetric analysis. The structural analysis of Zn-CPs shows that they are isostructural and present 2D sheet structures with 4-connected {44.62}-sql topology, which are further expanded into 3D supermolecular structures by H-bonding interaction. Furthermore, the luminescent experiments revealed that CPs 1 and 2 show highly sensitive and selective sensing for CrO42−/Cr2O72− anions and nitrofurantoin in aqueous medium.

Multi-functional fluorescent responses of cobalt complexes derived from functionalized amide-bridged ligand

Multi-functional fluorescent detection for inorganic pollutants and biological protein is important but challenging. In this work, five multi-functional luminescent coordination polymers (LCPs), [Co2(L)2(PDA)2]·H2O (1), [Co(L)(TPD)(H2O)2]·8H2O (2), [Co(L)(1,3-BDC)]·2H2O (3), [Co(L)(MIP)]·H2O (4) and [Co3(L)3(HIPA)3] (5) [H2PDA = 1,3-phenylenediacetic acid, H2TPD = 2,5-thiophenedicarboxylic acid, 1,3-H2BDC = 1,3-benzenedicarboxylic acid, H2MIP = 5-methylisophthalic acid and H2HIPA = 5-hydroxyisophthalic acid] have been successfully synthesized from a naphthalene-dicarboxamide [N,N′-bis(4-methylenepyridin-4-yl)-1,4-naphthalene dicarboxamide (L)] with multi-functional spacers. 1 and 2 show 4-c sql networks. 3–5 display mab, pcu and hxg 3D frameworks, respectively. The title complexes exhibit multi-functional fluorescent responses towards metal ion (Fe3+), anions (CrO42−, Cr2O72− and MnO4−) and biological protein (bovine serum albumin).