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Keywords = Coordination Polymers (CPs)

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11 pages, 3231 KiB  
Article
A Nitrogen-Rich Luminescent Zn(II) Coordination Polymer Based on a 2,4,6-Tris(di-2-pyridylamino)-1,3,5-triazine for Differential Fluorescent Sensing of Antibiotics in Aqueous Medium
by Sajeetha Parveen Banu, Mannanthara Kunhumon Noushija, Binduja Mohan and Sankarasekaran Shanmugaraju
Chemistry 2025, 7(4), 108; https://doi.org/10.3390/chemistry7040108 - 25 Jun 2025
Viewed by 521
Abstract
The design of suitable chemosensors for environmental pollutants and toxins detection at trace levels remains a critical area of research. Among various chemosensors, Zn(II) coordination polymers have garnered special interest as fluorescent probes for environmental applications. In this article, we report the synthesis [...] Read more.
The design of suitable chemosensors for environmental pollutants and toxins detection at trace levels remains a critical area of research. Among various chemosensors, Zn(II) coordination polymers have garnered special interest as fluorescent probes for environmental applications. In this article, we report the synthesis of a nitrogen-rich luminescent Zn(II) coordination polymer, TDPAT-Zn-CP, designed for differential fluorescent sensing of antibiotics in an aqueous medium. TDPAT-Zn-CP was synthesized using a star-shaped 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazine (TDPAT) fluorophore, a promising blue-emitting compound. The morphological and structural properties of TDPAT-Zn-CP were thoroughly analyzed using conventional spectroscopic and analytical techniques. The fluorescence titration studies in aqueous medium demonstrated that TDPAT-Zn-CP exhibits remarkable selectivity, sensitivity, and differential fluorescence sensing responses towards various antibiotics. Among the antibiotics tested, TDPAT-Zn-CP displayed a significant fluorescence quenching and high selectivity for sulfamethazine (SMZ), with a Stern–Volmer quenching constant of KSV = 1.68 × 104 M−1 and an impressive sensitivity of 4.95 ppb. These results highlight the potential of TDPAT-Zn-CP as a practically useful, highly effective polymeric sensor for the differential fluorescence-based detection of antibiotics in water, offering a promising approach for environmental monitoring and contamination control. Full article
(This article belongs to the Section Supramolecular Chemistry)
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15 pages, 2443 KiB  
Article
Thermally Stable Anilate-Based 3D CPs/MOFs
by Fabio Manna, Noemi Monni, Mariangela Oggianu, Juan Modesto Clemente-Juan, Miguel Clemente-León and Maria Laura Mercuri
Crystals 2025, 15(6), 570; https://doi.org/10.3390/cryst15060570 - 17 Jun 2025
Viewed by 272
Abstract
The synthesis and characterization of two novel redox-active MOFs/CPs based on 3d transition metal ions and 3,6-ditriazolyl-2,5-dihydroxybenzoquinone (trz2An) are reported herein. By combining trz2An with NiII and MnII ions via the hydrothermal method, two phases, formulated as [...] Read more.
The synthesis and characterization of two novel redox-active MOFs/CPs based on 3d transition metal ions and 3,6-ditriazolyl-2,5-dihydroxybenzoquinone (trz2An) are reported herein. By combining trz2An with NiII and MnII ions via the hydrothermal method, two phases, formulated as [Ni2(trz2An)2]·2.5H2O (1) and [Mn(trz2An)(H2O)]·1.5H2O (2), are obtained. Both compounds crystallize as neutral polymeric 3D frameworks, where the metal ions are coordinated through the oxygen atoms of the anilate linkers forming either straight (1) or zig-zag (2) 1D chains. In particular, (1) is a MOF, where these chains are connected through the nitrogen atom at the 4 position of the triazolyl group, which completes the coordination sphere of each metal ion, affording a 3D structure containing a void volume of 28.7% and voids that can be useful for the sorption of small molecules. Interestingly, (1) and (2) show a redox behavior due to the presence of the anilate linker, being reduced electrochemically in the −0.7 to −0.9 V range due to the benzoquinone–semiquinone one-electron reduction and magnetic behavior dominated by antiferromagnetic interactions in the anilate 1D chains. Full article
(This article belongs to the Section Macromolecular Crystals)
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10 pages, 2064 KiB  
Communication
Photocurrent, Photodegradation, and Proton Conductivity of the Stable Dipyridyl and Thiophene-Functionalized CuII2 Supramolecular Compound
by Jin-He Wang, Guang-Min Liang, Jiu-Yu Ji, Xiao-Jie Gong, Liang-Liang Huang, Li-Ping Zhao, Wen-Xuan Xie and Kun Zhou
Inorganics 2025, 13(6), 195; https://doi.org/10.3390/inorganics13060195 - 12 Jun 2025
Viewed by 465
Abstract
Due to its excellent visible light absorption characteristics, the photocurrent, photodegradation, and proton conductivity of the stable dipyridyl and thiophene-functionalized supramolecular compound [Cu2(TAA)4(4,4′-bpy)]n (CuII2 for short, HTAA = 2-thiopheneacetic acid, 4,4′-bpy = 4,4′-bipyridine) have been [...] Read more.
Due to its excellent visible light absorption characteristics, the photocurrent, photodegradation, and proton conductivity of the stable dipyridyl and thiophene-functionalized supramolecular compound [Cu2(TAA)4(4,4′-bpy)]n (CuII2 for short, HTAA = 2-thiopheneacetic acid, 4,4′-bpy = 4,4′-bipyridine) have been studied in detail. The current density of photocurrent of CuII2 is 1.87 μA·cm−2, and CuII2 degrades methylene blue (MB) with a degradation efficiency of 68.0% under xenon lamp. In addition, CuII2 shows remarkable proton conductivity of 1.79 × 10−3 S·cm−1 (at 75 °C and 98% relative humidity), superior to most copper(II)-based coordination polymers (CPs), and is expected to become a potential proton conductor in the future. Full article
(This article belongs to the Special Issue Supramolecular Chemistry: Prediction, Synthesis and Catalysis)
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11 pages, 2575 KiB  
Article
Concentration Gradient-Induced Syntheses and Crystal Structures of Two Copper(II) Coordination Polymer Based on Phthalic Acid and 2,2′-Bipyridine
by Tao Zhou, Gengyi Zhang, Chunhong Tan, Yong Liu and Xiao-Feng Wang
Molecules 2025, 30(9), 1953; https://doi.org/10.3390/molecules30091953 - 28 Apr 2025
Viewed by 507
Abstract
The reaction of copper nitrate, phthalic acid (1,2-H2BDC), and bipyridine in ammonia/ethanol media affords two multi-copper (II) cluster-based coordination polymers, namely {[Cu4(bpy)4(OH)2(BDC)2]·2OH·13H2O}n (USC-CP-6) and {[Cu2(BDC)2 [...] Read more.
The reaction of copper nitrate, phthalic acid (1,2-H2BDC), and bipyridine in ammonia/ethanol media affords two multi-copper (II) cluster-based coordination polymers, namely {[Cu4(bpy)4(OH)2(BDC)2]·2OH·13H2O}n (USC-CP-6) and {[Cu2(BDC)2(bpy)2(H2O)]·3H2O}n (USC-CP-7), under ambient conditions, with CP-6 forming at the bottom and CP-7 at the upper edge of the same beaker. The single-crystal structures reveal that it is a rare case of gradient-induced formation of different multi-copper(II) cluster-based CPs within a single-solution chemical reaction. CP-6 crystallizes in the monoclinic system, sp. gr. P21/c, and is composed of chair-like tetranuclear [Cu4(μ3-OH)2(bpy)4(BDC)2]2+ clusters as secondary building units, bridged by BDC2− ligands to form a two-dimensional layer framework, while CP-7 crystallizes in the monoclinic system, sp. gr. P21/n, with binuclear [Cu2(1,2-BDC)2(bpy)2(H2O)] clusters linked by bridging BDC2− ligands to form a one-dimensional looped double chain. Through intermolecular ππ stacking and hydrogen bonds between the coordination water, lattice water, and free oxygen atoms from carboxylate, both compounds yield a 3D supramolecular structure. Full article
(This article belongs to the Special Issue Reviews of Chemical Crystallography)
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20 pages, 4171 KiB  
Article
Efficient Photodegradation of Dyes from Single and Binary Aqueous Solutions Using Copper(II) Coordination Polymers
by Ildiko Buta, Maria Andreea Nistor and Simona Gabriela Muntean
Molecules 2025, 30(8), 1652; https://doi.org/10.3390/molecules30081652 - 8 Apr 2025
Cited by 1 | Viewed by 851
Abstract
The present study reports the application of three copper(II) coordination polymers, namely 1[Cu3L2(N3)] CH3COO (CP1), 1[Cu3L2(NO3)]NO3·2CH3OH·2H2O ( [...] Read more.
The present study reports the application of three copper(II) coordination polymers, namely 1[Cu3L2(N3)] CH3COO (CP1), 1[Cu3L2(NO3)]NO3·2CH3OH·2H2O (CP2), and 1[Cu3L2(H2O)](ClO4)2 (CP3), where H2L stands for N,N′-bis[(2-hydroxybenzilideneamino)propyl]-piperazine) as catalysts for photocatalytic degradation of Acid Orange 7 and Methyl Orange dyes from single and binary aqueous solutions. The influence of the photocatalyst nature, hydrogen peroxide presence, reaction time, dye concentration, and catalyst dose on the photodegradation efficiency was studied. Under visible light irradiation, complex CP1 demonstrated the highest photodegradation efficiency of 92.40% and 80.50% towards Acid Orange 7 and Methyl Orange, respectively. The kinetic studies indicated that the photodegradation process followed a pseudo-first-order kinetics. The highest rate of the degradation process was obtained when CP1 is used, and the necessary time for the degradation of the dyes increases with increasing concentration of the dye solutions. The degradation efficiency of more than 75% after five recycling/reuse cycles of CP1 and the yields higher than 72% obtained for the degradation of dyes from the binary system demonstrate the photocatalytic capacity of CP1. A photocatalytic oxidation mechanism was proposed and the stability of the CP1 complex before and after the photodegradation process of dyes, both from simple and binary solutions, was investigated and confirmed. Full article
(This article belongs to the Special Issue Study on Synthesis and Photochemistry of Dyes)
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38 pages, 43510 KiB  
Review
Coordination Polymers of Vanadium and Selected Metal Ions with N,O-Donor Schiff Base Ligands—Synthesis, Crystal Structure, and Application
by Dariusz Osypiuk, Agata Bartyzel and Beata Cristóvão
Molecules 2025, 30(5), 1104; https://doi.org/10.3390/molecules30051104 - 27 Feb 2025
Viewed by 1176
Abstract
This review provides an overview of the synthesis, characterization and application of coordination polymers based on N,O-donor Schiff base ligands. The coordination polymers (CPs) represent a novel class of inorganic–organic hybrid materials with tunable compositions and fascinating structures. They are [...] Read more.
This review provides an overview of the synthesis, characterization and application of coordination polymers based on N,O-donor Schiff base ligands. The coordination polymers (CPs) represent a novel class of inorganic–organic hybrid materials with tunable compositions and fascinating structures. They are composed of metal ions and organic ligands. Therefore, the nature of the metal ion and type of organic ligand is the most significant factor in constructing targeted coordination polymers with the desired properties. Due to the versatile coordination modes, N,O-donor Schiff base ligands are also used to construct various CPs. Full article
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15 pages, 3479 KiB  
Article
Synthesis, Crystal Structures, Hirshfeld Surface Analysis, Computational Investigations, Thermal Properties, and Electrochemical Analysis of Two New Cu(II) and Co(II) Coordination Polymers with the Ligand 5-Methyl-1-(pyridine-4-yl-methyl)-1H-1,2,3-triazole-4-carboxylate
by Markus Bergedahl, Pilar Narea, Jaime Llanos, Ruth Pulido, Nelson Naveas, Pilar Amo-Ochoa, Félix Zamora, Gerzón E. Delgado, Felipe M. Galleguillos Madrid, Yasna León and Iván Brito
Int. J. Mol. Sci. 2025, 26(4), 1671; https://doi.org/10.3390/ijms26041671 - 15 Feb 2025
Viewed by 1524
Abstract
Two new Cu(II) (CP1) and Co(II) (CP2) coordination polymers (CPs) with the triazole ligand 5-methyl-1-(pyridin-4-yl-methyl)-1H-1,2,3-triazole-4-carboxylate (L1) have been synthesized and structurally characterized by SCXRD (Single Crystal X-Ray Difraccion), PXRD (Power X-Ray Difracction), FT-IR (Fourier Transform Infrared), TG (Theermo Gravimetric), and electrochemical techniques. Both [...] Read more.
Two new Cu(II) (CP1) and Co(II) (CP2) coordination polymers (CPs) with the triazole ligand 5-methyl-1-(pyridin-4-yl-methyl)-1H-1,2,3-triazole-4-carboxylate (L1) have been synthesized and structurally characterized by SCXRD (Single Crystal X-Ray Difraccion), PXRD (Power X-Ray Difracction), FT-IR (Fourier Transform Infrared), TG (Theermo Gravimetric), and electrochemical techniques. Both CPs were obtained at the water/n-butanol interface by reacting nitrate salts of each metal with the NaL1 ligand. SCXRD analysis revealed that CP1 (Coordination Polymer 1) and CP2 (Coordination Polymer 2) crystallize in the monoclinic space groups C2/c (No. 15) and P21/n (No. 14), respectively, forming 1D zigzag chain structures, which further lead to a 2D supramolecular network through O-H⋯O and C-H⋯O hydrogen bond interactions, respectively. In CP1, the supramolecular structure is assembled by hydrogen bonds involving water molecules. In contrast, CP2 forms its supramolecular network mainly through hydrogen bonds between adjacent triazole ligand molecules. Hirshfeld surface analysis revealed that the most significant contributions to the crystal packing come from H⋯O/O⋯H, H⋯H, H⋯N/N⋯H, and H⋯C/C⋯H interactions. In addition, FT-IR provided information on the functional groups involved in the coordination, while the decomposition patterns of both CPs were evaluated by TGA. Electrochemical studies conducted in a saline environment showed that CP1 exhibits superior hydrogen evolution reaction (HER) kinetics compared to CP2, as evidenced by a higher exchange current density and a lower Tafel slope. Density functional theory calculations and experimental bandgap measurements provided a deeper understanding of the electronic properties influencing the electrochemical behavior. The results highlight the potential of CP1 as an efficient catalyst for HER under saline conditions. Full article
(This article belongs to the Section Physical Chemistry and Chemical Physics)
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40 pages, 9873 KiB  
Review
Luminescent Lanthanide Infinite Coordination Polymers for Ratiometric Sensing Applications
by Ziqin Song, Yuanqiang Hao, Yunfei Long, Peisheng Zhang, Rongjin Zeng, Shu Chen and Wansong Chen
Molecules 2025, 30(2), 396; https://doi.org/10.3390/molecules30020396 - 18 Jan 2025
Cited by 4 | Viewed by 1909
Abstract
Ratiometric lanthanide coordination polymers (Ln-CPs) are advanced materials that combine the unique optical properties of lanthanide ions (e.g., Eu3+, Tb3+, Ce3+) with the structural flexibility and tunability of coordination polymers. These materials are widely used in biological [...] Read more.
Ratiometric lanthanide coordination polymers (Ln-CPs) are advanced materials that combine the unique optical properties of lanthanide ions (e.g., Eu3+, Tb3+, Ce3+) with the structural flexibility and tunability of coordination polymers. These materials are widely used in biological and chemical sensing, environmental monitoring, and medical diagnostics due to their narrow-band emission, long fluorescence lifetimes, and excellent resistance to photobleaching. This review focuses on the composition, sensing mechanisms, and applications of ratiometric Ln-CPs. The ratiometric fluorescence mechanism relies on two distinct emission bands, which provides a self-calibrating, reliable, and precise method for detection. The relative intensity ratio between these bands varies with the concentration of the target analyte, enabling real-time monitoring and minimizing environmental interference. This ratiometric approach is particularly suitable for detecting trace analytes and for use in complex environments where factors like background noise, temperature fluctuations, and light intensity variations may affect the results. Finally, we outline future research directions for improving the design and synthesis of ratiometric Ln-CPs, such as incorporating long-lifetime reference luminescent molecules, exploring near-infrared emission systems, and developing up-conversion or two-photon luminescent materials. Progress in these areas could significantly broaden the scope of ratiometric Ln-CP applications, especially in biosensing, environmental monitoring, and other advanced fields. Full article
(This article belongs to the Special Issue Nano-Functional Materials for Sensor Applications—2nd Edition)
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29 pages, 4508 KiB  
Review
Metal-Coordinated Polymer–Inorganic Hybrids: Synthesis, Properties, and Application
by Shaghayegh Abtahi, Nayanathara Hendeniya, Sharif Tasnim Mahmud, Gabriel Mogbojuri, Chizoba Livina Iheme and Boyce Chang
Polymers 2025, 17(2), 136; https://doi.org/10.3390/polym17020136 - 8 Jan 2025
Cited by 3 | Viewed by 2241
Abstract
This review examines the recent advancements and unique properties of polymer–inorganic hybrid materials formed through coordination bonding (Class II hybrids), which enable enhanced functionality and stability across various applications. Here, we categorize these materials based on properties gained through complexation, focusing on electrical [...] Read more.
This review examines the recent advancements and unique properties of polymer–inorganic hybrid materials formed through coordination bonding (Class II hybrids), which enable enhanced functionality and stability across various applications. Here, we categorize these materials based on properties gained through complexation, focusing on electrical conductivity, thermal stability, photophysical characteristics, catalytic activity, and nanoscale self-assembly. Two major synthetic approaches to making these hybrids include homogeneous and heterogeneous methods, each with distinct tradeoffs: Homogeneous synthesis is straightforward but requires favorable mixing between inorganic and polymer species, which are predominantly water-soluble complexes. In contrast, heterogeneous methods are post-processing techniques that provide high area selectivity for inorganic precursors, allowing precise integration within polymer matrices. Finally, we highlight the role of hybrid linkers, namely metallosupramolecular polymers, in creating structural diversity. These can be organized into three main groups: metal–organic frameworks (MOFs), coordination polymers (CPs), and supramolecular coordination complexes (SCCs). Each of these groups introduces unique structural and functional properties that expand the potential applications of hybrid materials. Full article
(This article belongs to the Section Smart and Functional Polymers)
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27 pages, 14209 KiB  
Article
Statistical and Block Copolymers of n-Dodecyl and Allyl Isocyanate via Titanium-Mediated Coordination Polymerization: A Route to Polyisocyanates with Improved Thermal Stability
by Maria Iatrou, Aikaterini Katara, Panagiotis A. Klonos, Apostolos Kyritsis and Marinos Pitsikalis
Polymers 2024, 16(24), 3537; https://doi.org/10.3390/polym16243537 - 19 Dec 2024
Viewed by 936
Abstract
Well-defined amorphous/semi-crystalline statistical copolymers of n-dodecyl isocyanate, DDIC, and allyl isocyanate, ALIC, were synthesized via coordination polymerization using the chiral half-titanocene complex CpTiCl2(O-(S)-2-Bu) as an initiator. In the frame of the terminal model, the monomer reactivity ratios of the statistical copolymers [...] Read more.
Well-defined amorphous/semi-crystalline statistical copolymers of n-dodecyl isocyanate, DDIC, and allyl isocyanate, ALIC, were synthesized via coordination polymerization using the chiral half-titanocene complex CpTiCl2(O-(S)-2-Bu) as an initiator. In the frame of the terminal model, the monomer reactivity ratios of the statistical copolymers were calculated using both well-known linear graphical methods and the computer program COPOINT. The molecular and structural characteristics of the copolymers were also calculated. The thermal properties of these samples were studied by differential scanning calorimetry, DSC, measurements. The kinetics of the thermal decomposition of the statistical copolymers was studied by thermogravimetric analysis, TGA, and differential thermogravimetry, DTG, and the activation energy of this process was calculated by employing several theoretical models. Moreover, block copolymers with the structure P[DDIC-b-(DDIC-co-ALIC)] were synthesized by sequential addition of monomers and coordination polymerization methodologies. The samples were characterized by nuclear magnetic resonance, NMR, spectroscopy; size exclusion chromatography, SEC; and DSC. The thermal stability of the blocks was also studied by TGA and DTG and compared to the corresponding statistical copolymers, showing that the macromolecular architecture greatly affects the properties of the copolymers. A thiol-ene click post-polymerization reaction was performed to introduce aromatic groups along the polyisocyanate chain in order to improve the thermal stability of the parent polymers. Evidently, these statistical and block copolymers can be employed as precursors for the synthesis of novel polyisocyanate-based materials. Full article
(This article belongs to the Special Issue Emerging Trends in Polymer Engineering: Polymer Connect-2024)
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10 pages, 2942 KiB  
Article
Synthesis, Structure, and Properties of 2D Lanthanide(III) Coordination Polymers Constructed from Cyclotriphosphazene-Functionlized Hexacarboxylate Ligand
by Qi Jia, Yicheng Yao, Xiaoming Zhu, Juntao Wang, Zeyu Li, Liudi Ji and Peng Hu
Molecules 2024, 29(23), 5602; https://doi.org/10.3390/molecules29235602 - 27 Nov 2024
Cited by 2 | Viewed by 986
Abstract
The design and synthesis of novel lanthanide-based coordination polymers (Ln-CPs) from flexible organic ligands is still attractive and challenging. In this work, two isostructural Ln-CPs with a unique 2D network, namely, [Ln2(H3L)2(DMF)]]n (Ln = Dy for [...] Read more.
The design and synthesis of novel lanthanide-based coordination polymers (Ln-CPs) from flexible organic ligands is still attractive and challenging. In this work, two isostructural Ln-CPs with a unique 2D network, namely, [Ln2(H3L)2(DMF)]]n (Ln = Dy for 1, Tb for 2) based on a flexible polycarboxylic acid ligand hexakis(4-carboxylato-phenoxy)cyclotriphosphazene (H6L), have been solvothermally synthesized and structurally characterized. Significantly, it is the first observation of polycarboxylic acid ligands participating in coordination in the construction of coordination polymers in the form of semi-deprotonation. Magnetic measurements showed the presence of field-induced slow magnetic relaxation in complex 1. The luminescence property of 2 had been studied in the solid state at room temperature. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry 2.0)
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8 pages, 2827 KiB  
Communication
Coordination of O-Propyl-N-phenylthiocarbamate to HgI2 and the Crystallographic Characterization of an Anilinium Chloride Thiocarbamate Adduct
by Wafa Arar, Nuri Ekici, Michael Knorr, Isabelle Jourdain, Carsten Strohmann and Jan-Lukas Kirchhoff
Molbank 2024, 2024(4), M1923; https://doi.org/10.3390/M1923 - 22 Nov 2024
Viewed by 1028
Abstract
In order to investigate the coordination chemistry of O-alkyl N-aryl thiocarbamate ligands, HgI2 was reacted with one equivalent of PrOC(=S)N(H)Ph L in toluene solution to afford the 1D polymeric title compound [{IHg(μ-I)}{κ1-PrOC(=S)N(H)Ph}]n CP1. The formation [...] Read more.
In order to investigate the coordination chemistry of O-alkyl N-aryl thiocarbamate ligands, HgI2 was reacted with one equivalent of PrOC(=S)N(H)Ph L in toluene solution to afford the 1D polymeric title compound [{IHg(μ-I)}{κ1-PrOC(=S)N(H)Ph}]n CP1. The formation of this iodide-bridged coordination polymer was ascertained by a single-crystal X-ray diffraction study performed at 100 K, as well as the formation of an adduct between anilinium chloride and L forming a supramolecular ribbon of composition [L(PhNH3)(Cl)]. The occurrence of anilinium chloride is due to the partial hydrolysis of L in the presence of HCl. Full article
(This article belongs to the Section Organic Synthesis and Biosynthesis)
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11 pages, 4511 KiB  
Article
A Series of Rare-Earth Metal-Based Coordination Polymers: Fluorescence and Sensing Studies
by Nian-Hao Wang, Jin-Mei Liu, Bin Tan and Zhao-Feng Wu
Sensors 2024, 24(21), 6867; https://doi.org/10.3390/s24216867 - 25 Oct 2024
Viewed by 1111
Abstract
Ratiometric fluorescent sensing based on dual-emitting fluorescent coordination polymers (FL-CPs) has attracted intense attention due to their sensing accuracy and easy visualization when compared with sensing relying solely on monochromatic FL-CPs. In this work, a series of rare-earth metal-based CPs, formuled as [(CH [...] Read more.
Ratiometric fluorescent sensing based on dual-emitting fluorescent coordination polymers (FL-CPs) has attracted intense attention due to their sensing accuracy and easy visualization when compared with sensing relying solely on monochromatic FL-CPs. In this work, a series of rare-earth metal-based CPs, formuled as [(CH3)2NH2][Ln(bpdc)2] (Ln3+ = Y3+, Eu3+ and Tb3+, H2bpdc = biphenyl-4,4′-dicarboxylic acid), are presented, which show dual emission aroused from the Ln3+ ions and the inefficient intermolecular energy transfer from ligands to Ln3+ metals. For clarity, the as-made Ln-CPs are named Eu-bpdc, Tb-bpdc, and Y-bpdc based on the corresponding Ln3+. Notably, Eu-bpdc, presented as an example, could be used as FL sensing material ratiometric to Fe3+ ions. The ratio of FL intensity of Eu3+ ions to bpdc2− ligands (I415/I615) showed a good linear relationship with the concentrations of Fe3+ ions. Moreover, the detection process could be visibly monitored through a change from purple to blue when Eu-bpdc was used as an FL proble. This work provides a good example for exploring visibly ratiometric sensors based on FL-CPs. Full article
(This article belongs to the Special Issue Colorimetric and Fluorescent Sensors and Their Application)
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16 pages, 5685 KiB  
Article
A Dy(III) Coordination Polymer Material as a Dual-Functional Fluorescent Sensor for the Selective Detection of Inorganic Pollutants
by Ying Wang, Baigang An, Si Li, Lijiang Chen, Lin Tao, Timing Fang and Lei Guan
Molecules 2024, 29(18), 4495; https://doi.org/10.3390/molecules29184495 - 22 Sep 2024
Viewed by 1169
Abstract
A Dy(III) coordination polymer (CP), [Dy(spasds)(H2O)2]n (1) (Na2Hspasds = 5-(4-sulfophenylazo)salicylic disodium salt), has been synthesized using a hydrothermal method and characterized. 1 features a 2D layered structure, where the spasda3− anions act as [...] Read more.
A Dy(III) coordination polymer (CP), [Dy(spasds)(H2O)2]n (1) (Na2Hspasds = 5-(4-sulfophenylazo)salicylic disodium salt), has been synthesized using a hydrothermal method and characterized. 1 features a 2D layered structure, where the spasda3− anions act as pentadentate ligands, adopting carboxylate, sulfonate and phenolate groups to bridge with four Dy centers in η3-μ1: μ2, η2-μ1: μ1, and monodentate coordination modes, respectively. It possesses a unique (4,4)-connected net with a Schläfli symbol of {44·62}{4}2. The luminescence study revealed that 1 exhibited a broad fluorescent emission band at 392 nm. Moreover, the visual blue color has been confirmed by the CIE plot. 1 can serve as a dual-functional luminescent sensor toward Fe3+ and MnO4 through the luminescence quenching effect, with limits of detection (LODs) of 9.30 × 10−7 and 1.19 × 10−6 M, respectively. The LODs are relatively low in comparison with those of the reported CP-based sensors for Fe3+ and MnO4. In addition, 1 also has high selectivity and remarkable anti-interference ability, as well as good recyclability for at least five cycles. Furthermore, the potential application of the sensor for the detection of Fe3+ and MnO4 was studied through simulated wastewater samples with different concentrations. The possible sensing mechanisms were investigated using Ultraviolet-Visible (UV-Vis) absorption spectroscopy and density functional theory (DFT) calculations. The results revealed that the luminescence turn-off effects toward Fe3+ and MnO4 were caused by competitive absorption and photoinduced electron transfer (PET), and competitive absorption and inner filter effect (IFE), respectively. Full article
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19 pages, 9210 KiB  
Article
Influence of Metal Ions on the Structural Complexity of Mixed-Ligand Divalent Coordination Polymers
by Fang-Ju Cheng, Kai-Min Wang, Chia-Yi Lee, Song-Wei Wang, Kedar Bahadur Thapa, Manivannan Govindaraj and Jhy-Der Chen
Chemistry 2024, 6(5), 1020-1038; https://doi.org/10.3390/chemistry6050059 - 14 Sep 2024
Cited by 1 | Viewed by 1621
Abstract
The reactions of the angular ligand 4,4′-oxybis(N-(pyridin-3-yl)benzamide) (L1) and 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) with divalent metal salts yielded three distinct coordination polymers (CPs): {[Zn2(L1)(1,4-NDC)2]·MeOH}n, 1, {[Cu(L [...] Read more.
The reactions of the angular ligand 4,4′-oxybis(N-(pyridin-3-yl)benzamide) (L1) and 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) with divalent metal salts yielded three distinct coordination polymers (CPs): {[Zn2(L1)(1,4-NDC)2]·MeOH}n, 1, {[Cu(L1)(1,4-NDC)(H2O)]·3H2O}n, 2, and {[Cd(L1)(1,4-NDC)]·2H2O}n, 3. Complex 1 features a 2-fold interpenetrated 3D framework with the (412·63)-pcu topology, while complex 2 reveals a 1D triple-strained helical chain and complex 3 displays a 3-fold interpenetrated 3D framework with (66)-dia topology. Additionally, the reactions of the flexible ligand N,N′-bis(3-methylpyridyl) adipoamide (L2) afforded {[Co4(L2)0.5(1,4-NDC)3(H2O)33-OH)2]·EtOH·2H2O}n, 4, {[Zn2(L2)(1,4-NDC)2]·2CH3OH}n, 5, and [Cd(L2)(adipic)(H2O)]n (H2adipic = adipic acid), 6, exhibiting a self-catenated 3D framework with the (420·68)-8T32 topology, a 2D layer with the (413·62) − (4,4)IIb topology, and a 2D layer with the (44·62)-sql topology, respectively. The structural diversity observed in complexes 16 highlights the pivotal influence of the metal center on the degree of entanglement in CPs within mixed-ligand systems. The thermal stability and luminescent properties of complexes 13, 4, and 6 are also discussed. Full article
(This article belongs to the Section Inorganic and Solid State Chemistry)
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