Comparative Study on the Proton Conduction Behaviors of Two Acidic Amphiphilic and Hydrophilic Coordination Compounds in Nafion Composite Membranes.

The acidic amphiphilic compound H[Co(H2L1)(HL1)(phen)]·3H2O (H4(Co-L1), H3L1 = 5-(3', 5'-dicarboxylphenyl)-pyridine-2-carboxylic, phen = phenanthroline) and the hydrophilic compound [Ni(HL2)(H2O)5]·H2O (H(Ni-L2), H3L2 = 5-(3',5'-dicarboxylphenyl)-pyridine-3-carboxylic) were synthesized via hydrothermal reactions at acidic conditions. The acidity of H4(Co-L1) is stronger than of H(Ni-L2); while the hydrogen bond continuity in H4(Co-L1) extended monodirectionally, which is smaller compared to the three-directional extension observed in H(Ni-L2). The proton conduction behaviors of these two compounds as fillers of Nafion composite membranes have been investigated. The results indicate that the optimal doping amounts of H4(Co-L1) and H(Ni-L2) are 2 and 1%, respectively; the proton conductivities of H4(Co-L1)/Nafion-2 and H(Ni-L2)/Nafion-1 composite membranes are 0.243 and 0.212 S·cm-1, respectively, which are approximately 50.2 and 30.6% higher than that of pure Nafion membrane, respectively. A higher doping amount of H4(Co-L1) can be attributed to its hydrophobic phen ligand, which promotes compatibility with Nafion membrane and reduces aggregation. Hydrogen bond continuity has a more significant effect on proton conductivity than acidity at relatively low doping amounts; conversely, this relationship reverses at relatively high doping amounts.

Cd-MOF and Its Ln3+-Post Modification Products: Regulation of Luminescence Properties and Improved Detection of Uric Acid, Quinine, and Quinidine.

One 3D Cd-MOF, namely, {[(HDMA)2][Cd3(L)2]·5H2O·2DMF}n (LCU-124, LCU indicates Liaocheng University), was synthesized from an ether-containing ligand 1,3-bis(3,5-dicarboxylphenoxy)benzene (H4L). Its Ln3+-postmodified samples, Eu3+@LCU-124 and Tb3+@LCU-124, were obtained through cation exchange of dimethylamine cation (HDMA) with Eu3+ and Tb3+. The successful entry of rare earth into LCU-124 by cation exchange modification was verified by IR, XRD, XPS, EDS mapping, and luminescence spectra. The proportion of Eu3+/Tb3+ was adjusted during the modification process, leading to fluorescent materials with different emissions. Luminescence measurements indicated that these complexes exhibited interesting multiresponsive sensing activities toward biomarkers urine acid (UA), quinine (QN), and quinidine (QND). First, LCU-124 has a pronounced quenching effect toward UA with the detection limit of 31.01 µM. After modification, the visualization of the detection was improved significantly and the detection limit of Eu3+@LCU-124 was reduced to 0.868 µM. Second, when QN and QND were present in the suspensions of Eu3+@LCU-124 and Tb3+@LCU-124, strong blue light emission peaks occurred, while the characteristic emission of Eu3+/Tb3+ decreased, forming ratiometric fluorescent sensors with the detection limit in the range of 0.199-9.49 µM. The fluorescent probes have high selectivity, excellent sensitivity recycling, and fast response time (less than 1 min). Besides, a simple logic gate circuit and a range of luminescent mixed matrix membranes were designed to provide simple and fast detection of above biomarkers. Our work indicated that modification of Eu3+/Tb3+ could improve the detection ability significantly.

Construction of Coordination Spaces with Narrow Pore Windows in Co-Based Metal-Organic Frameworks toward CO2/N2 Separation.

Carbon emission reduction is an important measure to mitigate the greenhouse effect, which has become a hotspot in global climate change research. To contribute to this, here, we fabricated two Co-based metal-organic frameworks (Co-MOFs), namely, {[Co3(NTB)2(bib)]·(DMA)2·(H2O)4}n (DZU-211) and {[Co3(NTB)2(bmip)]·(DMA)2}n (DZU-212) (H3NTB = 4,4',4″-nitrilotribenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane, bmip = 1,3-bis(2-methyl-1H-imidazol-1-yl)propane) to realize efficient CO2/N2 separation by dividing coordination spaces into suitable pores with narrow windows. DZU-211 reveals a 3D open porous framework, while DZU-212 exhibits a 3D double-fold interpenetrated structure. The two MOFs both possess large coordination spaces and small open pore sizes, via the bib ligand insertion and framework interpenetration, respectively. Comparatively, DZU-211 reveals superior selective CO2 uptake properties due to its more suitable pore characteristics. Gas sorption experiments show that DZU-211 has a CO2 uptake of 52.6 cm3 g-1 with a high simulated CO2/N2 selectivity of 101.7 (298 K, 1 atm) and a moderate initial adsorption heat of 38.1 kJ mol-1. Moreover, dynamic breakthrough experiments confirm the potential application of DZU-211 as a CO2 separation material from postcombustion flue gases.

Notably Stable Bifunctional Europium-Centered Metal-Organic Framework for Instant Sensing of Uric Acid and 1-Hydroxypyrene in Human Urine.

A new Eu-centered metal-organic framework, [(CH3)2NH2][Eu(cdip)(H2O)] (compound 1), was fabricated by the reaction of Eu(NO3)3·6H2O and a high-symmetry ligand, 5,5'-carbonyldiisophthalic acid (H4cdip). Interestingly, compound 1 exhibits extraordinary stability, including air, thermal, and chemical stabilities, in an aqueous solution with a broad pH range of 1-14, which is rarely seen in the field of metal-organic framework materials. Notably, compound 1 is proved to be an exceptional prospective luminescent sensor for recognizing 1-hydroxypyrene and uric acid both in DMF/H2O solution and human urine with a fast response (1-HP: 10 s; UA: 80 s), high quenching efficiency Ksv (7.01 × 104 M-1 for 1-HP and 5.46 × 104 M-1 for UA in DMF/H2O solution; 2.10 × 104 M-1 for 1-HP and 3.43 × 104 M-1 for UA in human urine), low limit of detection (1.61 µM for 1-HP and 0.54 µM for UA in DMF/H2O solution; 0.71 µM for 1-HP and 0.58 µM for UA in human urine), and remarkable anti-interference ability based on luminescence-quenching effects observable by the naked eye. This work provides a new strategy for the exploration of potential luminescent sensors based on Ln-MOFs for 1-HP, UA, or other biomarkers in biomedical and biological fields.

Detection Enhancement of One Multifunctional Cd-Metal-Organic Framework toward Tetracycline Antibiotics by Simply Mixing Eu3+ in Suspension.

It is necessary to find more simple methods to improve the detection selectivity and sensitivity of antibiotics. Herein, we constructed a novel three-dimensional (3D) Cd-MOF LCU-117 assembled from p-terphenyl-4,2″,5″,4'-tetracarboxylic acid, which showed a special 3D helical structure with carboxylic acid ligands and nitrogen-containing ligands crossing each other vertically. Luminescence measurements indicated that LCU-117 has high selectivity and sensitivity toward Eu3+ through the ratiometric effect. Meanwhile, this complex itself could detect antibiotics oxytetracycline (OTC) through the turn-off mechanism. When Eu3+ was added in suspensions of LCU-117 (noted as Eu3+@LCU-117), the detection toward OTC was enhanced significantly and visually. The sensing mechanism was investigated in detail by various measurements and theoretical calculations. LCU-117 has a good effect on the logic gate, potential fingerprint detection, and mixed-matrix membranes (MMMs). The practical application for monitoring OTC in water samples also provided a satisfactory result.

Two Co-Based Metal-Organic Framework Isomers with Similar Metal-Carboxylate Sheets: Turn-On Ratiometric Luminescence Sensing Activities toward Biomarker N-Acetylneuraminic Acid and Discrimination of Ga3+ and In3.

Two supramolecular Co-MOF isomers, namely, {[Co(L)0.5(m-bimb)]·3H2O}n (LCU-115) and {[Co(L)0.5(p-bimb)]·3H2O}n (LCU-116), were synthesized from an amide-containing carboxylic acid N,N″-(3,5-dicarboxylphenyl)benzene-1,4-dicarboxamide (H4L) and two flexible positional isostructural N-containing ligands m-bimb and p-bimb (m-bimb = 1,3-bis((1H-imidazol-1-yl)methyl)benzene; p-bimb = 1,4-bis((1H-imidazol-1-yl)methyl)benzene). The carboxylate ligands connect Co(II) centers to form 2D metal-carboxylate sheets, which are extended further by m-bimb and p-bimb to form a 2D bilayer with parallel stacking (LCU-115) and a 3D framework (LCU-116), respectively. Luminescence measurements indicated that these two complexes exhibited interesting multiresponsive sensing activities toward pH, biomarker N-acetylneuraminic acid, and trivalent cations Ga3+/In3+. They show highly sensitive turn-on fluorescence responses in the acidic range and can also be regarded as on-off-on vapoluminescent sensors to typical acidic and basic gases HCl and Et3N. It is worth noting that these complexes have excellent turn-on ratiometric fluorescence sensing ability for N-acetylneuraminic acid (NANA) with detection limits as low as 7.39 and 8.06 µM, respectively. Furthermore, they were successfully applied for the detection of NANA in simulated urine and serum samples with satisfactory results. For ion detection, LCU-116 could detect both Ga3+ and In3+, while LCU-115 could distinguish Ga3+ from In3+ with the latter showing luminescence quenching. The sensing mechanism was investigated in detail by XRD, UV-vis, EDS, XPS, SEM, and TEM. The results of interday and intraday precision studies gave low RSD values in the range of 1.19-3.53%, ascertaining the reproducibility of these sensors. The recoveries for the sensing analytes in simulated urine/serum or real water are satisfactory from 96.7 to 103.3% (toward NANA) and 96.6 to 115.0% (toward Ga3+ and In3+), indicating that these two complexes also possess acceptable reliability for monitoring in real samples. The results indicated that the supramolecular isomers LCU-115 and LCU-116 are promising material candidates for application in biological and environmental monitoring.

Series of Dual Functional Two-Dimensional RE-OFs for Nitrophenol Reduction and Dye Separation.

The rational design and preparation of stable and multifunctional metal-organic frameworks (MOFs) with excellent catalysis and adsorption properties are desirable but are great challenges. The nitrophenol (NP) reduction to aminophenols (APs) by using the catalyst Pd@MOFs is an effective strategy, which has attracted extensive attention in recent years. Here, we report four stable isostructural two-dimensional (2D) rare earth metal-organic frameworks [RE4(AAPA)6(DMA)2 (H2O)4][DMA]3[H2O]8 (namely LCUH-101, RE = Eu, Gd, Tb, Y; AAPA2- = 5-[(anthracen-9-yl-methyl)-amino]-1,3-isophthalate), which feature a 2D layer structure with sql topology of point symbol {44·62} and exhibit excellent chemical stability and thermostability. The as-synthesized Pd@LCUH-101 was utilized for the catalytic reduction of 2/3/4-nitrophenol, which indicates high catalytic activity and recyclability attributed to the synergistic effect between Pd nanoparticles and the 2D layered structure. Of note, the turnover frequency (TOF), the reaction rate constant (k), and the activation energy (Ea) of Pd@LCUH-101 (Eu) in the reduction of 4-NP, respectively, are 1.09 s-1, 2.17 min-1, and 50.2 kJ·mol-1, which show that it has superior catalytic activity. Remarkably, LCUH-101 (Eu, Gd, Tb, and Y) are multifunctional MOFs that can effectively absorb and separate mixed dyes. The appropriate interlayer spacing enables them to efficiently adsorb methylene blue (MB) and rhodamine B (RhB) in aqueous solution, with adsorption capacities of 0.97 and 0.41 g·g-1, respectively, which is one of the highest values among those of the reported MOF-based adsorbers. Meanwhile, LCUH-101 (Eu) can be used for the separation of the dye mixture MB/MO and RhB/MO, and the excellent reusability enables LCUH-101 (Eu) to be used as chromatographic column filters to quickly separate and recover dyes. Therefore, this work provides a new strategy for the exploitation of stable and efficient catalysts for NP reduction and adsorbents for dyes.

Two-Dimensional Lanthanide Metal-Organic Frameworks as a Platform for Sensing Pollutant and Nitrophenols Reduction.

The discharge of harmful and toxic pollutants in water is destroying the ecosystem balance and human being health at an alarming rate. Therefore, the detection and removal of water pollutants by using stable and efficient materials are significant but challenging. Herein, three novel lanthanide metal-organic frameworks (Ln-MOFs), [La(L)(DMF)2(H2O)2]·H2O (LCUH-104), [Nd(L)(DMF)2(H2O)2]·H2O (LCUH-105), and [Pr(L)(DMF)2(H2O)2]·H2O (LCUH-106) [H3L = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid (H3TZI)] were solvothermally constructed and structurally characterized. In the three Ln-MOFs, dinuclear metallic clusters {Ln2} were connected by deprotonated tetrazol-containing dicarboxylate TZI3- to obtain a 2D layered framework with a point symbol of {42·84}·{46}. Their excellent chemical and thermal stabilities were beneficial to carry out fluorescence sensing and achieve the catalytic nitrophenols (NPs) reduction. Especially, the incorporation of the nitrogen-rich tetrazole ring into their 2D layered frameworks enables the fabrication of Pd nanocatalysts (Pd NPs@LCUH-104/105/106) and have dramatically enhanced catalytic activity by using the unique metal-support interactions between three Ln-MOFs and the encapsulating palladium nanoparticles (Pd NPs). Specifically, the reduction of NPs (2-NP, 3-NP, and 4-NP) in aqueous solution by Pd NPs@LCUH-104 exhibits exceptional conversion efficiency, remarkable rate constants (k), and outstanding cycling stability. The catalytic rate of Pd NPs@LCUH-104 for 4-NP is nearly 8.5 times more than that of Pd/C (wt 5%) and its turnover frequency value is 0.051 s-1, which indicate its excellent catalytic activity. Meanwhile, LCUH-105, as a multifunctional fluorescence sensor, exhibited excellent fluorescence detection of norfloxacin (NFX) (turn on) and Cr2O72- (turn off) with high selectivity and sensitivity at a low concentration, and the corresponding fluorescence enhancement/quenching mechanism has also been systematically investigated through various detection means and theoretical calculations.

A "Pre-Division Metal Clusters" Strategy to Mediate Efficient Dual-Active Sites ORR Catalyst for Ultralong Rechargeable Zn-Air Battery.

To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal-air batteries, catalysts with dual-active centers have stood out. Here, a "pre-division metal clusters" strategy is firstly conceived to fabricate a N,S-dual doped honeycomb-like carbon matrix inlaid with CoN4 sites and wrapped Co2 P nanoclusters as dual-active centers (Co2 P/CoN4 @NSC-500). A crystalline {CoII 2 } coordination cluster divided by periphery second organic layers is well-designed to realize delocalized dispersion before calcination. The optimal Co2 P/CoN4 @NSC-500 executes excellent 4e- ORR activity surpassing the benchmark Pt/C. Theoretical calculation results reveal that the CoN4 sites and Co2 P nanoclusters can synergistically quicken the formation of *OOH on Co sites. The rechargeable Zn-air battery (ZAB) assembled by Co2 P/CoN4 @NSC-500 delivers ultralong cycling stability over 1742 hours (3484 cycles) under 5 mA cm-2 and can light up a 2.4 V LED bulb for ≈264 hours, evidencing the promising practical application potentials in portable devices.

Enhancing Proton Conductivity of Nafion Membrane by Incorporating Porous Tb-Metal-Organic Framework Modified with Nitro Groups.

A rigid carboxylate ligand with a nitro functional group was selected to coordinate with Tb(III) cation, and Tb-MOF ({[Tb4(L)4(OH)4(H2O)3]·8H2O}n, H2L = 2-nitroterephthalic acid) with large porous and excellent hydrophilicity was obtained successfully. The obtained Tb-MOF was filled into the Nafion matrix to improve its proton conduction performance. The Tb-MOF/Nafion composite membrane was characterized by PXRD, IR, and thermogravimetry (TG) and for water uptake, area swelling, and proton conductivity. The activity energy, Ea, value of the composite membrane, which is a very important factor affecting the proton conduction performance of the membrane, was fitted and calculated. It was revealed that Tb-MOF can improve the proton conductivities of composite membranes, and the improvement degree and Ea value were both affected by Tb-MOF content. When Tb-MOF content was 5%, the proton conductivity of the composite membrane was 1.53 × 10-2 S·cm-1 at 100% RH and 80 °C, which is 1.81 times that of the pure Nafion membrane. A MOF containing a nitro functional group was first doped into Nafion in this study and exhibited excellent performance for improving composite membrane proton conductivity. This study will provide a valuable reference for designing different functionalized MOFs to promote the proton conductivities of proton exchange membranes.

Two Multiresponsive Luminescent Zn-MOFs for the Detection of Different Chemicals in Simulated Urine and Antibiotics/Cations/Anions in Aqueous Media.

Two Zn-MOFs, namely, {[Zn(L)0.5(bpea)]·0.5H2O·0.5DMF}n [LCU-113 (for Liaocheng University)] and {[Zn(L)0.5(ibpt)]·H2O·DMF}n (LCU-114), were synthesized based on flexible tetracarboxylic acid 1,3-bis(3,5-dicarboxyphenoxy)benzene (H4L) and different N-ligands [bpea = 1,2-dipyridyl ethane; ibpt = 3-(4'-imidazolobenzene)-5-(pyridine-4'-yl)-1,2,4-triazole]. LCU-113 and LCU-114 possess twofold interpenetrating three-dimensional pillared layer structures, in which a two-dimensional layer formed by carboxylic acid and Zn2+ ions was pillared by bpea and ibpt, respectively. The two complexes show high water stability and high luminescence sensing performance toward organic solvents, ions, and antibiotics, as well as chemicals, in simulated urine. The investigation showed that (1) LCU-113 and LCU-114 could detect uric acid (UA, 2,6,8-trihydroxypurine, metabolite of purine) and p-aminophenol (PAP, biomarker of phenamine) in simulated urine by luminescence quenching, respectively, and (2) luminescence quenching of LCU-113 and LCU-114 occurred in aqueous solutions of nitrofurazone (NZF), Fe3+, and CrO42-/Cr2O72-. All the above detections have excellent anti-interference ability and recyclability. The luminescence mechanism analysis indicates that weak interactions between the framework structures and the target analytes as well as the energy competition (inner filter effect) play an important role in sensing the above analytes. The practical application for monitoring NZF/Fe3+ in water samples was also tested.

Series of TM-OFs as a Platform for Efficient Catalysis and Multifunctional Luminescence Sensing.

Three novel porous transition-metal-organic frameworks (TM-OFs), formulated as [Co3(DCPN)2(µ2-OH2)4(H2O)4](DMF)2 (1), [Cd3(DCPN)2(µ2-OH2)4(H2O)4](DMF)2 (2), and [CdK(DCPN)(DMA)] (3), have been successfully prepared via solvothermal conditions based on a 5-(3',6'-dicarboxylic phenyl) nicotinic carboxylic acid (H3DCPN) ligand. 1 and 2 both have the same porous 3D network structure with the point symbol of {410·614·84}·{45·6}2 based on trinuclear ({Co3} or {Cd3}) clusters, indicating a one-dimensional porous channel, and possess excellent water and thermal stability; 3 also displays a porous 3D network structure with a 4-connected sra topology based on the heteronuclear metal cluster {CdK}. Complex 1 can be used to load Pd nanoparticles (Pd NPs) via a wetness impregnation strategy to obtain Pd@1. The reduction of nitrophenols (2-NP, 3-NP, 4-NP) by Pd@1 in aqueous solution shows outstanding conversion, excellent rate constants (k), and remarkable cycling stability due to the synergistic effect of complex 1 and Pd NPs. Luminescence sensing tests confirmed that 2 is a reliable multifunctional chemical sensor with high selectivity and sensitivity for low concentrations of Fe3+, Cr2O72-, CPFX, and NFX. Specifically, 2 shows a fluorescence enhancement behavior toward fluoroquinolone antibiotics (CPFX and NFX), which has not been reported previously in the literature. Moreover, the rational mechanism of fluorescence sensing was also systematically investigated by various detection means and theoretical calculations.

Monitoring Gases Content in Modern Agriculture: A Density Functional Theory Study of the Adsorption Behavior and Sensing Properties of CO2 on MoS2 Doped GeSe Monolayer.

The reasonable allocation and control of CO2 concentration in a greenhouse are very important for the optimal growth of crops. In this study, based on density functional theory (DFT), an MoS2-GeSe monolayer was proposed to unravel the issues of the lower selectivity, poorer sensitivity and non-recyclability of traditional nanomaterial gas sensors. The incorporation of MoS2 units greatly enhanced the sensitivity of the pure GeSe monolayer to CO2 and the high binding energy also demonstrated the thermal stability of the doped structures. The ideal adsorption energy, charge transfer and recovery time ensured that the MoS2-GeSe monolayer had a good adsorption and desorption ability. This paper aimed to solve the matter of recycling sensors within agriculture. This research could provide the theoretical basis for the establishment of a potentially new generation of gas sensors for the monitoring of crop growth.

Fabrication of a Stable Europium-Based Luminescent Sensor for Fast Detection of Urinary 1-Hydroxypyrene Constructed from a Tetracarboxylate Ligand.

A novel europium-centered metal-organic framework fabricated from a symmetric and rigid ligand with tetracarboxylate groups, 2,6-di(2',5'-dicarboxylphenyl)pyridine (H4ddpp), has been synthesized solvothermally. Characterized by single-crystal X-ray diffraction, compound 1 features a 3D microporous structure with a butterfly-shaped trinuclear Eu3(COO)6 secondary building unit. Interestingly, three kinds of 1D open channels viewed in different directions in compound 1 are discovered, and the void ratio is calculated to be 47.5% by PLATON software. Solid-state luminescent experiments at 298 K reveal that compound 1 displays naked-eye characteristic red emission of Eu3+ ions monitoring the typical 5D0 → 7F2 transition. The exploration of luminescent sensing tests discloses that compound 1 has an outstanding capacity for recognizing urinary 1-hydroxypyrene (1-HP) with a quite fast response and high sensitivity, giving the quenching efficiency of 98.2% after the immersion time for just 1 min and 73.2% with the amount of 1-HP only 0.05 mg/mL. To our knowledge, it is the first reported Eu-MOF as an extremely fast-responsive and highly sensitive luminescent sensor for 1-HP which is interference-free from other urinary components. Furthermore, the successful preparation of the luminescent test papers makes compound 1 convenient, easy, and real-time in the application for sensing 1-HP in biomedical and biological fields.

Silica-Organometallic One-Dimensional Hybrid Employing a Ag-πC═C Bond Connecting Alternating Ag4(NO3)4 and Octavinylsilsesquioxane.

Layering AgNO3 in alcohol onto octavinylsilsesquioxane (OVS) in CHCl3 results in a one-dimensional coordination polymer, {Ag4(NO3)4(OVS)·solvents}n (SD/Ag4a-d), consisting of unprecedented flat weakly bonded Ag4(NO3)4 alternating with the firmly covalent OVS through AgI-πC═C bonds. The preferential assembling medium for SD/Ag4a is proven to be alcohols, where a 4:1 silver-OVS adduct is detected by electrospray ionization mass spectrometry. The present outcomes may assist our knowledge of particular interactions for supramolecular architectures of a polynuclear silver system built from OVS containing eight pendent olefin tails.

Nanocage-Based N-Rich Metal-Organic Framework for Luminescence Sensing toward Fe3+ and Cu2+ Ions.

Luminescent metal-organic frameworks (LMOFs) as sensors showing highly efficient detection toward toxic heavy-metal ions are in high demand for human health and environmental protection. A novel nanocage-based N-rich LMOF (LCU-103) has been constructed and characterized. It is a 2-fold interpenetrating structure built from N-rich {Zn6(dttz)4} nanocages extended by N-donor ligand Hdpa [H3dttz = 4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazole; Hdpa = 4,4'-dipyridylamine]. Notably, LCU-103 contains abundant N functional sites anchoring on both the windows of nanocages and the inner channels of the framework that can interact with metal ions and then recognize them. As a result, it can serve as a luminescent sensing material for detecting trace amounts of Fe3+ and Cu2+ ions with low limits of detection (LODs) of 1.45 and 1.66 µM, respectively, through a luminescent quenching mechanism. Meanwhile, LCU-103 as a LMOF sensor exhibits several advantages such as high sensitivity, appropriate selectivity (for Fe3+ in H2O), recycling stability, and fast response times in N,N-dimethylformamide. Moreover, LCU-103 also displays good luminescent quenching activity toward Fe3+ in H2O and a simulated 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid biological system with low LODs of 1.51 and 1.52 µM, respectively. LCU-103 test papers were further prepared to offer easy and real-time detection of Fe3+ and Cu2+ ions. Importantly, when density functional theory calculations and multiple experimental evidence, including X-ray photoelectron spectroscopy, UV-vis absorption, luminescence decay lifetimes, and quantum efficiencies, are combined, a preferred N-donor site and possible weak interaction sensing mechanism is also proposed to elucidate the quenching effect.

Polyoxometalate-Derived Multi-Component X/W2 C@X,N-C (X=Co, Si, Ge, B, and P) Nanoelectrocatalysts for Efficient Triiodide Reduction in Dye-Sensitized Solar Cells.

Multi-component tungsten carbide-based hybrid materials featuring different heteroatom dopants coated with X,N dual-doped carbon layers (X/W2 C@X,N-C, XWXNC) were prepared by selecting Keggin-type polyoxometalates (POMs) (NH4 )n [XW12 O40 ] (X=Co, Si, Ge, B, and P) and dicyandiamide (DCA) as precursors. The electrocatalytic activity of these nanocomposites as counter electrode (CE) catalysts for dye-sensitized solar cells (DSSCs) was systematically investigated. Structure characterizations show that X,N heteroatoms were successfully introduced into the W2 C and carbon frameworks. The obtained X,N dual-doped carbon layers were modified and loaded with W2 C nanoparticles, promoting the improvement of catalytic performance by a synergistic effect. The consequence of photoelectric conversion efficiency (PCE) is CoWCoNC (6.68 %)>SiWSiNC (6.56 %)>GeWGeNC (6.49 %)>BWBNC (6.45 %)>PWPNC (6.20 %)>WNC (6.05 %). With the increase in electronegativity of the dopants, the photovoltaic performance decreases in a reverse order. This work provides a shortcut to the rational design of highly efficient and cost-effective catalysts for DSSCs.

Structural Diversity of Copper(I) Cluster-Based Coordination Polymers with Pyrazine-2-thiol Ligand.

Six novel copper(I) cluster-based coordination polymers (CPs) [Cu9(pzt)7Cl2]n (1), [Cu2(pzt)Cl]n (2), [Cu4(pzt)3Br]n (3), [Cu(pzt)]n (4), [Cu4(pzt)3I]n (5), and [Cu7(pzt)6I]n (6) were solvothermally synthesized using Hpzt (Hpzt = pyrazine-2-thiol) ligand and well-characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD). Six CPs exhibit either 2D (4 and 6) or 3D (1-3, and 5) network based on diverse multinuclear {CuxSy} clusters. The structural evolutions of 1-6 are greatly influenced by types of metal halides and the ligand-to-metal molar ratio used in the reaction. Among them, compound 1 displays interesting temperature-dependent photoluminescence arising from triplet cluster-centered (3CC) excited state from the cluster metal core. Compounds 1-6 also exhibit photocurrent responses upon visible-light illumination (λ = 420 nm) in the order 6 > 5 > 3 > 1 > 4 > 2. This work not only shows the structural diversity of {CuxSy} clusters-based CPs but also provides an interesting insight into structural modulation using crystal engineering concept.

Multiresponsive Luminescent Sensitivities of a 3D Cd-CP with Visual Turn-on and Ratiometric Sensing toward Al3+ and Cr3+ as Well as Turn-off Sensing toward Fe3.

By using the reduced Schiff base tricarboxylate ligand H3cip, one novel 3D Cd-based coordination polymer (Cd-CP) with the formula [Cd(Hcip)(bpea)0.5(H2O)]n (H3cip = 5-(3-carboxybenzylamino)isophthalic acid, bpea = 1,2-bis(4-pyridyl)ethane) has been solvothermally synthesized. The prepared Cd-CP possesses a 4-connected CdSO4 net based on dinuclear {Cd2} units. Luminescence measurements revealed that the complex exhibited ratiometric turn-on luminescence responses toward Al3+ and Cr3+ with a significant color change, which could be easily distinguished by the naked eye under ultraviolet light. Cd-CP can also respond to Fe3+ through a turn-off mechanism. Interestingly, the luminescence quenched by Fe3+@Cd-CP can be recovered and increased significantly by adding some competitive Al3+, while Cr3+ can only marginally increase the luminescence intensity of Fe3+@Cd-CP. Moreover, the detection of the three aforementioned metal ions can be realized by using Cd-CP-coated test papers, extending the potential application regions of the reported material to point-of-care tests and environmental field studies.

Space Craft-like Octanuclear Co(II)-Silsesquioxane Nanocages: Synthesis, Structure, Magnetic Properties, Solution Behavior, and Catalytic Activity for Hydroboration of Ketones.

Two novel space craft-like octanuclear Co(II)-silsesquioxane nanocages, {Co8[(MeSiO2)4]2(dmpz)8} (SD/Co8a) and {Co8[(PhSiO2)4]2(dmpz)8} (SD/Co8b) (SD = SunDi; Hdmpz = 3,5-dimethylpyrazole), have been constructed from two similar multidentate silsesquioxane ligands assisted with a pyrazole ligand. The Co8 skeleton consists of eight tetrahedral Co(II) ions arranged in a ring and is further capped by two (MeSiO2)4 ligands up and down. The auxiliary dmpz- ligands seal the ring finally. Electrospray ionization mass spectrometry revealed SD/Co8a and SD/Co8b are highly stable in CH2Cl2. Magnetic analysis implies that SD/Co8a announces antiferromagnetic interactions between Co(II) ions. Moreover, both of them display good homogeneous catalytic activity for hydroboration of ketones in the presence of pinacolborane under mild conditions.