In recent years, coordination polymers (CPs) have emerged as versatile scaffolding materials built from various metal ions and organic ligands, and these materials are highly investigated for their use in numerous applications. In particular, coordination polymers including lanthanide ions (Ln) are very promising because these ions transfer some interesting luminescence features to the frameworks, such as sharp emission, long lifetimes, large Stokes' shift and high color purity. Although much research focusses on carboxylate-type ligands for the preparation of coordination polymers owing to their ability to form porous structures, organophosphonates appear to be promising ligands as well. In fact they display higher coordination versatility and they are able to bridge a large number of metal cations enhancing the metal density and allowing for the introduction of multiple functionalities in the heterometallic structures. Moreover, thanks to the proton exchange properties of the phosphonate groups, these materials can display remarkable proton conduction properties. In the current review, lanthanide phosphonates assembling 1-, 2- and 3-dimensional (D) coordination polymers are described, and their value in different applications will be outlined. From the literature survey, it emerges that 1D structures with an extended hydrogen-bonding network were the most promising materials for proton conduction, while 2D structures were mainly investigated for their luminescent and magnetic properties. In many examples the luminescence of 3D lanthanide coordination polymers could be changed by incorporating small molecules or metal ions, which opens up new possibilities for their use as straightforward sensor materials. 

Lanthanide phosphonate coordination polymers

Two novel microporous anionic lanthanide metal-organic frameworks (Ln-MOFs), namely {[(CH3)2NH2][Ln(bptc)]·2H2O}n (Ln = Gd (1) and Dy (2), H4bptc = biphenyl-3,3',5,5'-tetracarboxylic acid) with a new 4,8-connected topology have been synthesized and structurally characterized. Ln-MOF 1 shows a significant magnetocaloric effect with -ΔSmaxm = 26.37 J kg-1 K-1 at 2 K for ΔH = 7 T, and a high proton conductivity of 1.02 × 10-4 S cm-1 at 323 K and 90% RH. Moreover, Ln-MOF 1 shows specific selective adsorption of the cationic dye Rhodamine B. Ln-MOF 2 exhibits field-induced slow magnetic relaxation with an energy barrier (Ueff) of 48.19 K, characteristic emission of Dy3+, and selective adsorption of Rhodamine B. Therefore, 2 is a multifunctional Ln-MOF with magnetic, fluorescence and selective adsorption properties.

Anionic lanthanide metal-organic frameworks with magnetic, fluorescence, and proton conductivity properties and selective adsorption of a cationic dye.

In this work, a novel Mn(II) chain coordination polymer (Mn-CP), {[Mn(iip)(2bbpum)0.5(H2O)3]·2H2O}n [H2iip = 5-iodoisophthalic acid, 2bbpum = N,N′-bis(2-pyridinemethyl)oxamide] was synthesized under ambient conditions. Mn-CP further assembles into a 3D supramolecular architecture through hydrogen bonds, halogen bonds, and ππ stacking interactions. The composite Mn-CP/nafion membrane has low activation energy for proton transfer, which results in its temperature-insensitive proton conductivity. The cyclic voltammetry demonstrates that the Mn-CP electrode (Mn-CP/GCE) shows quite different redox properties in 0.1 M H2SO4 and 0.1 M PBS aqueous solutions. The Mn-CP/GCE exhibits a couple of irreversible redox peaks with an oxidation peak potential suitable for the nitrite oxidation in 0.1 M H2SO4. Quite differently, in the PBS aqueous buffer solution, the Mn-CP electrode has a couple of irreversible redox peaks. The reduction peak potential is appropriate for the H2O2 reduction. So, the Mn-CP/GCE can be used not only in the electrocatalytic oxidation of NO2– but also in the electrocatalytic reduction of H2O2. The amperometric response reveals that the Mn-CP/GCE exhibits high-selective and extremely sensitive oxidation sensing of NO2– and reduction sensing of H2O2. The exponential detection range is 0.01–20 mM for NO2– and 0.01–10.5 mM for H2O2. The linear detection range for both H2O2 and NO2– is 0.01–0.10 mM. The detection limit is 1.865 μM for NO2– and 8.57 μM for H2O2. The Mn-CP/GCE exhibits high electrochemical stability and fine reproducibility. Moreover, the strategy can be translated to a portable screen-printed electrode (SPE). The Mn-CP/SPE shows more sensitive sensing to NO2– and H2O2 than Mn-CP/GCE. Moreover, it can detect NO2– and H2O2 efficiently in the real-world samples. So, Mn-CP may be a potential dual nonenzymatic electrochemical sensory material for NO2–via oxidation sensing and H2O2via reduction sensing. 

Proton-Conductive and Electrochemical-Sensitive Sensing Behavior of a New Mn(II) Chain Coordination Polymer

Syntheses, crystal structures, topology and dual electronic behaviors of a family of amine-templated three- dimensional zinc-organophosphonate hybrid solids

In this work, we design and synthesize one organic molecule solid-state material and three metal–organic frameworks, (H3tcpb·H2O)n (H3tcpb-H2O), [Mn2(Htcpb)(μ3-SO4)(H2O)2]·H2O}n (1), {[Co(Htcpb)(H2O)3]·0.5CH3CN·H2O}n (2), and {[Ni(Htcpb)(H2O)3]·H2O}n (3), based on 2-(6-phenyl-[2,3′-bipyridin]-4-yl)benzene-1,3,5-tricarboxylic acid (H3tcpb) to study their proton transport pathways and conducting mechanisms. The electrochemical experimental results demonstrated that the finest proton conductivity (σ) value of 1 modified by sulfate anions can reach as high as 5.83 × 10–3 S·cm–1 being approximately three times greater than that of H3tcpb-H2O (1.90 × 10–3 S·cm–1). Meanwhile, the finest σ values of two isomeric 2 and 3 being 3.14 × 10–3 and 3.08 × 10–3 S·cm–1, respectively, are also higher than the value of H3tcpb-H2O. This report demonstrates that the finest σ values of H3tcpb-H2O and 1–3 are all in line with the demand for high-protonic conductors, which sparks us to bring about better proton-conducting crystalline materials. 

Water-Mediated Proton Conduction in Metal–Organic Frameworks with High Water Stability Constructed by a Terpyridine Tricarboxylate Ligand

Two lanthanide coordination polymers (CPs) {[Er(Hmtbd)(H2mtbd)(H2O)3]·2H2O}n (1) and [Yb(Hmtbd)(H2mtbd)(H2O)3]n (2) carrying an N-heterocyclic carboxylate ligand 5-(3-methylformate-1H-1,2,4-triazole-1-methyl)benzen-1,3-dicarboxylate (H3mtbd) were prepared under solvothermal conditions. The single-crystal X-ray diffraction data demonstrate that 1 and 2 are isostructural and display 1D chain structure. Alternating current (AC) impedance measurements illustrate that the highest proton conductivities of 1 and 2 can attain 5.09 × 10-3 and 3.09 × 10-3 S·cm-1 at 100 °C and 98% relative humidity (RH), respectively. The value of 1 exceeds those of most reported lanthanide-based crystalline materials and ranks second among the described Er-CPs under similar conditions, whereas the value for 2 is the highest proton conductivity among the previous Yb-CPs. Coupled with the structural analyses of the two CPs and H2O vapor adsorption, the calculated Ea values help to deduce their proton conductive mechanisms. Notably, the N-heterocyclic units (triazole), carboxyl, and hydrogen-bonding network all play key roles in the proton-transfer process. The prominent proton conductive abilities of both CPs show great promise as efficient proton conductors.

High Proton Conduction in Two Highly Water-Stable Lanthanide Coordination Polymers from a Triazole Multicarboxylate Ligand.

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High Proton Conduction in Two Highly Water-Stable Lanthanide Coordination Polymers from a Triazole Multicarboxylate Ligand.