Coordination Polymers Research Articles

Engineering highly reactive nanoarray based on tetrazole-triazole coordination polymer and ammonium perchlorate for advanced energetic microchips

The energetic microchips can be obtained through the integration of energetic materials into microelectromechanical systems (MEMS). Herein, a novel MEMS-compatible energetic composite Cutztr@AP has been prepared by using an in-situ approach. The recrystallized ammonium perchlorate (AP) is uniformly confined within the voids among the Cutztr24 nanorod arrays, resulting in a close contact between Cutztr24 and AP. This structure may effectively improve the mass transfer between the oxidizer and the fuels, thereby enhancing the reactivity. Morphological analysis reveals a uniform distribution of AP within the Cutztr@AP12.5 structure. Consequently, the heat release obtained from non-isothermal decomposition of Cutztr@AP12.5 is 1628 J/g, surpassing the independent heat release from Cutztr24 and AP combined. Benefiting from the enhanced reactivity of Cutztr@AP12.5, a significantly shorter flame duration (190 ms) was obtained with a larger luminous radiation area exceeding 2.5 cm2 comparison to Cutztr24, which has a flame duration of 673 ms with a luminous radiation area of around 1.0 cm2. More importantly, integrating Cutztr@AP12.5 into the energetic microchip reduces the ignition energy to approximately 19.0 mJ, as compared to 25.9 mJ for pure Cutztr24. This study offers a unique method for constructing high-performance energetic microchips.

Affordable Two-Dimensional Layered Cd(II) Coordination Polymer: High-Performance Pseudocapacitor Electrode Behavior.

In recent years, pseudocapacitive materials have been investigated rigorously as they provide a unique pathway for realizing high-energy and high-power densities. However, innovative approaches involving rational design and synthesis of new materials are still vital to address concerns such as degradation, low conductivity, low cycling performance, high resistance, production cost, etc. Working in this direction, we report the cost-effective synthesis, characterization, and excellent pseudocapacitive behavior of a Cd(II)-based coordination polymer (COP) abbreviated as Cd(DAB). It has been realized in quantitative yield through a facile one-pot reaction occurring among the N4-ligand, 3,3'-diaminobenzidine (DAB), and Cd(II) ions, derived from Cd(OAc)2·2H2O, at room temperature. The proposed structure of the COP was ascertained by subjecting it to various standard spectroscopic and electron microscopic studies; these techniques reveal the self-assembly of indefinitely long coordination strands into a two-dimensional (2D) layered structure. The electrochemical performance of Cd(DAB) was evaluated as an electrode material for supercapacitors. Owing to its high conductivity, it portrayed remarkable energy storage (pseudocapacitor) behavior; it exhibited a high specific capacitance of 1341.6 F g-1 and a long cycle life with 81% retention over 10,000 cycles at 20 A g-1. Additionally, an asymmetrical supercapacitor device was fabricated, which exhibited a specific capacitance of 428.5 F g-1 at a current density of 1 A g-1.

An Unprecedented Tridentate-Bridging Coordination Mode of Permanganate Ions: The Synthesis of an Anionic Coordination Polymer-[CoIII(NH3)6]n[(K(κ1-Cl)2(μ2,2',2″-(κ3-O,O',O″-MnO4)2)n∞]-Containing Potassium Central Ion and Chlorido and Permanganato Ligands.

A unique compound (compound 1) with structural features including an unprecedented tridentate-bridging coordination mode of permanganate ions and an eight-coordinated (rhombohedral) κ1-chlorido and tridentate permanganato ligand in a potassium complex containing coordination polymer (CoIII(NH3)6]n[(K(κ1-Cl)2(μ2,2',2″-(κ3-O,O',O″-MnO4)2)n∞) with isolated regular octahedral hexamminecobalt(III) cation was synthesized with a yield of >90%. The structure was found to be stabilized by mono and bifurcated N-H∙∙∙Cl and N-H∙∙∙O (bridging and non-bridging) hydrogen bonds. Detailed spectroscopic (IR, far-IR, and Raman) studies and correlation analysis were performed to assign all vibrational modes. The existence of a resonance Raman effect of compound 1 was also observed. The thermal decomposition products at 500 °C were found to be tetragonal nano-CoMn2O4 spinel with 19-25 nm crystallite size and KCl. The decomposition intermediates formed in toluene at 110 °C showed the presence of a potassium- and chloride-containing intermediates combined into KCl during aqueous leaching, together with the formation of cobalt(II) nitrate hexahydrate. This means that the CoIII-CoII redox reaction and the complete decomposition of the permanganate ions occurred in the first decomposition step, with a partial oxidation of ammonia into nitrate ions.

Homochiral Zn(Ⅱ) coordination polymers with helixes constructed from semirigid lactate deriatives for circular polarization luminescence and fluorescent prober

In the presence of nitrogen heterocyclic compound 2,5-di(1H-imidazole-1 -yl)pyridine (2,5-DIP), luminescent chiral synthons (R)-H3CTA and (S)–H3CTA assembled with Zn2+ ions to obtain enantiomers [Zn((R)-HCTA) (2,5-DIP)]n (HU14-R) and [Zn((S)-HCTA) (2,5-DIP)]n (HU14–S)) under hydrothermal condition, respectively. Partially deprotonated (R)-HCTA2- anions were bridged by Zn2+ ions to form small left-handed (R)-HCTA-Zn chain in HU14-R, while (S)-HCTA2- anions and Zn2+ ions were connected together resulting in enantiomeric right-handed chain in HU14–S. Moreover, larger left-handed (R)-HCTA-Zn-2,5-DIP chain and right-handed (S)-HCTA-Zn-2,5-DIP chain were found in HU14-R and HU14–S, respectively. These helical building blocks were joined together to create a pair of 3D frameworks with dia net, which show strong fluorescent characteristic and circular dichroism response. Further tests proved that HU14-R and HU14–S have circularly polarized light (CPL) activity and their luminescence anisotropy factors (g1um) at 358 nm are +0.00346 and −0.00157, respectively. Moreover, as fluorescent probes, they have high stability, reliability and interference detection rate, and detection limits are up to 2.80 × 10−6 M for Cr2O72− and 6.19 × 10−6 M for MnO4−.

Crystal Structure, Photophysical Properties and Antibacterial Activity of a Cd(II) Complex with Trans-2,3,4-Trimethoxycinnamic Acid and 4,4'-Bipyridine Ligands.

A new coordination polymer {[Cd(C12H13O5)2(4,4'-bpy)(H2O)2]}n (Cd-Tmca-bpy) was constructed with trans-2,3,4-Trimethoxycinnamic acid (HTmca) and 4,4'-Bipyridine (4,4'-bpy) ligands. This complex was structurally characterized on the basis of elemental analysis, infrared (IR) spectroscopy, powder X-ray diffraction and thermogravimetric analyses. X-ray crystallography revealed that the complex was monoclinic, space group C2/c. The Cd(II) ion in the complex was six coordinated, adopting an octahedron geometry. The neighboring Cd(II) ions linked linear ligand 4,4'-bpy molecules to form an infinite 1D chain. The 1D chain was further interlinked by O-H···O and C-H···O hydrogen bonds, resulting in a 3-D supramolecular framework. Meanwhile, the photoluminescence spectrum of the Cd(II) complex at room temperature exhibited an emission maximum at 475 nm. Using the time-dependent density functional theory (TD-DFT) method, the electronic absorption spectra of the Cd(II) complex was predicted. A good agreement was achieved between the predicted spectra and the experimental data. Bioactivity studies showed that the complex exhibited significant inhibition halos against Pseudomonas aeruginosa (P. aeruginosa) and Staphylococcus aureus (S. aureus).

Fast and scalable preparation of metal–organic coordination polymeric precursor for bifunctional electrocatalysts for high performance lithium–oxygen batteries

The Metal-organic coordination polymers (MOCPs) with structural and functional diversity are considered effective cathode materials for Lithium-oxygen batteries (LOBs). Conventional synthesis methods make it difficult to obtain large quantities of materials. Here, A highly active low-cost Co-decorated N-doped carbon oxygen cathode catalyst (Co–N–C) was synthesized using a fast and scalable method based on positive and negative charge coordination. Rapid synthesis of MOCPs depends on the addition of base sites. A theory of “Lewis’s base-assisted rapid synthesis” was proposed. Co-N-C as LOBs air cathode showed 150 cycles with 1000 mAh g-1 at 500 mA g-1. The fast and scalable synthesis method can provide a feasible strategy for large-scale production of oxygen electrocatalysts for LOBs.

Synthesis, crystal structure, and thermal properties of energetic complex Cu(II) and Ag(I) based on 3-amino-4-(4,5-diamino-1,2,4-triazole-3yl)-furazan

High nitrogen compounds have received much attention due to their great potential as high energy density materials, and the selection of high nitrogen heterocyclic rings as ligands for energetic coordination compounds (ECCs) play a leading role in regulating the energy properties of ECCs. Furazan is rarely used as a building block for the development of high-energy metal ligands. In this study, a new type of high nitrogen ligand 3-amino-4-(4,5-diamino-1,2,4-triazole-3yl)-furazan (ATF) was selected and four kinds of high energy coordination polymers [Cu(II)(ATF)2·4H2O](NO3)2·2H2O (1), [Cu(II)(ATF)2·4H2O](ClO4)2·2H2O (2), [Ag(I)(ATF)2]ClO4·H2O (3) and [Ag(I)(ATF)2NO3] (4) were prepared by water solvent volatilization method and characterized for the first time. The single crystal XRD confirmed that there were abundant hydrogen bond interactions in the four complexes, resulting in dense aggregation with densities of 1.680 ∼ 2.089 g·cm−3. Meanwhile, theoretical calculations show that the detonation velocities of the four ECCs, 7578 ∼ 8192 m·s−1. In terms of thermal stability, the decomposition temperatures of the four ECCs (Td: 253 ∼ 288 °C) showed higher thermal stability during the rapid heating process than the reported ECCs (Cu(PZCA)2(ClO4)2, [Ag+(daf)NO3−]n and CHHP). Both shock and friction sensitivities are greater than 20 J and 300 N. This new structural motif is a promising high-energy material. Moreover, they can promote the combustion decomposition of ammonium perchlorate (AP) well, and the promotion effect of 1 and 2 is better than that of 3 and 4. In the field of explosives and propellants, four ECCs can be attractive candidates.

Upgrading Structural Conjugation in Three-Dimensional Ni-Based Metal-Organic Frameworks for Promoting Electrical Conductivity and Specific Capacitance.

Metal-organic frameworks (MOFs) have emerged as promising candidates for electrochemical energy storage and conversion due to their high specific surface areas, abundant active sites, and excellent chemical and structural tunability. However, the direct utilization of MOFs as electrochemical materials is a challenge because of the poor electroconductivity induced by the insulating nature of most organic linkers. Herein, a conjugated three-dimensional Ni-MOF {Ni(HBTC)(BPE)}n (Ni-BPE) with a 2-fold interpenetrating structure was developed via the coordination polymerization of Ni2+, a H3BTC ligand (1,3,5-benzenetricarboxylic acid), and a vinyl-functionalized bipyridine linker (1,2-di(4-pyridyl)ethylene, BPE). Ni-BPE displayed an enhanced conjugation system compared to analogous and insulated Ni-BPY that is constructed by the Ni-BTC layer and ordinary bipyridine linker (4,4'-bipyridine, BPY). Notably, upgrading structural conjugation promoted a dramatical ∼204 times increase in the electroconductivity of Ni-BPE compared to Ni-BPY. More importantly, Ni-BPE displayed a higher specific capacitance of 633.2 F g-1 (316.6 C g-1) at 1 A g-1, which exhibited a significant ∼1.5-fold enhancement than Ni-BPY. Furthermore, the asymmetric supercapacitor can reach a good energy density of 25.2 Wh kg-1 with a reasonable cycle stability of 71.0% over 5000 cycles. This work provides an effective method for optimizing the structure of insulating MOFs to enhance the electroconductivity and specific capacitance.

Temperature dependent self-assembly of lanthanide coordination polymers based on a benzimidazolium dicarboxylate linker: synthesis, structure and luminescence properties

Five new coordination polymers, namely [Ln(L)(NO3)2]n (Ln = La (1), Pr (2) and Sm (3)), [Eu(L)(NO3)2·1.5H2O]n (4) and [Tb(L)(OAc)2(H2O)·3H2O]n (5) (HOAc = CH3COOH), were synthesised by reaction of lanthanide nitrates with 1,3-bis(4-carboxybenzyl)benzimidazolium chloride (H2L+Cl−) under solvothermal conditions. All the coordination polymers were characterised by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, elemental analysis and single crystal X-ray diffraction. Complexes 1–5 exhibit two different 2-D structures due to the variation in reaction temperature. Complexes 1–4 are isostructural and crystallised in the monoclinic system, C2/c space group, showing a two-dimensional layer with Ln chains linked by L− ligands. Complex 5 crystallised in the P21/n space group, featuring a 2-D layer different from 1–4 with Tb dimers linked by L− ligands through carboxylates. Further, the luminescence properties of complexes 3–5 were investigated. In addition, the fluorescence lifetime and quantum efficiency of complex 4 were measured.

Four novel coordination polymers with beautiful three-dimensional frameworks as potential Fe3+/Cr2O72− sensors

Protecting water resources is the innate obligation of human beings, and detecting pollutants in water is an important work to protect water resources. In this work, we have prepared four novel coordination polymers, named {[Zn3(L)2(H2O)4]‧5H2O}n (1), {[Zn6(L)4(4,4′-bpy)(H2O)6]‧3H2O}n (2), [Cd(HL)(H2O)]n (3) and [Cd3(L)2(pyz)(H2O)3]n (4) (H3L = 1-(3-carboxybenzyl)-1H-pyrazole-3,5-dicarboxylic acid, 4,4′-bpy = 4,4′-bipyridine and pyz = pyrazine). The organic ligands exhibit various coordination patterns, making the beautiful structures of the four compounds quite different. Compounds 1, 2, and 4 all show three core clusters and form the final three-dimensional frameworks by interconnecting metal clusters and organic ligands. Meanwhile, compound 3 displays the infinite metal chain and forms the final three-dimensional framework. These four compounds were also used to detect cations/anions in the water, showing that they can selectively detect Fe3+ and Cr2O72−. The excellent anti-interference ability, limit of detection, and reproducibility suggest that these four compounds are all potential sensing materials for Fe3+ and Cr2O72−.

Micronuclear battery based on a coalescent energy transducer.

Micronuclear batteries harness energy from the radioactive decay of radioisotopes to generate electricity on a small scale, typically in the nanowatt or microwatt range1,2. Contrary to chemical batteries, the longevity of a micronuclear battery is tied to the half-life of the used radioisotope, enabling operational lifetimes that can span several decades3. Furthermore, the radioactive decay remains unaffected by environmental factors such as temperature, pressure and magnetic fields, making the micronuclear battery an enduring and reliable power source in scenarios in which conventional batteries prove impractical or challenging to replace4. Common radioisotopes of americium (241Am and 243Am) are α-decay emitters with half-lives longer than hundreds of years. Severe self-adsorption in traditional architectures of micronuclear batteries impedes high-efficiency α-decay energy conversion, making the development of α-radioisotope micronuclear batteries challenging5,6. Here we propose a micronuclear battery architecture that includes a coalescent energy transducer by incorporating 243Am into a luminescent lanthanide coordination polymer. This couples radioisotopes with energy transducers at the molecular level, resulting in an 8,000-fold enhancement in energy conversion efficiency from α decay energy to sustained autoluminescence compared with that of conventional architectures. When implemented in conjunction with a photovoltaic cell that translates autoluminescence into electricity, a new type of radiophotovoltaic micronuclear battery with a total power conversion efficiency of 0.889% and a power per activity of 139 microwatts per curie (μW Ci-1) is obtained.

Structural Diversity and Dimensionality of Three Cu(II)-dpds-C5O5 2- Coordination Polymers Controlled by the Coordination Sphere of Cu(II) Centers and the Coordination Modes of C5O5 2- (dpds = 4,4'-Dipyridyldisulfide).

Three supramolecular architectures, [Cu2(dpds)2(C5O5)2(H2O)4]·3H2O (1), [Cu(dpds)(C5O5)]·3H2O (2), and [Cu2(dpds)2(C5O5)2]·9H2O·C2H5OH (3) (dpds = 4,4'-dipyridyldisulfide and C5O5 2- (croconate) = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione), have been synthesized and structurally characterized. Compound 1 contains two crystallographically independent Cu(II) ions, which are both distorted octahedral geometry with elongation along the croconate- and H2O-bound axial positions and bonded with two N atoms of two dpds, two O atoms of one C5O5 2-, and two H2O molecules. Two crystallographically independent dpds ligands, both adopting the bis-monodentate bridging mode, connect two Cu(II) ions to form a one-dimensional zigzag chain-like coordination polymer. In 2 and 3, there are two and three crystallographically independent Cu(II) ions, respectively, which are all distorted octahedral geometries with elongation along the croconate-bound axial positions six-coordinated and bonded with two N atoms of two dpds ligands in cis- or/and trans-forms and four O atoms of two C5O5 2- ligands. The dpds ligands in 2 and 3 all adopt the bis-monodentate bridging mode, and the C5O5 2- ligands act as bridging ligands with bridging bis-bidentate through three C5O5 2- oxygen atoms in 2 and bridging bis-bidentate through four adjacent C5O5 2- oxygen atoms in 3, respectively, linking the Cu(II) ions to generate a two-dimensional layered and a three-dimensional metal-organic framework, respectively. The structural diversity and dimensionality observed in 1-3 may be attributed to the cis- or/and trans-coordination sphere of Cu(II) centers with two dpds ligands and the coordination modes of croconate ligands. Thermal stability and in situ temperature-dependent structural variations of 1-3 have been verified by thermogravimetric analysis and powder X-ray diffraction measurements. Compounds 1 and 3 both exhibit water vapor capture behaviors with hysteresis isotherms.

Statement of Retraction: Synthesis, characterization and anti-lung cancer activity of two transition metal coordination polymers based on the imidazole-containing ligands

Statement of Retraction: Synthesis, characterization and anti-lung cancer activity of two transition metal coordination polymers based on the imidazole-containing ligands

Highly Efficient Synergistic Chemotherapy and Magnetic Resonance Imaging for Targeted Ovarian Cancer Therapy Using Hyaluronic Acid-Coated Coordination Polymer Nanoparticles.

The diagnosis and treatment of ovarian cancer (OC) are still a grand challenge, more than 70% of patients are diagnosed at an advanced stage with a dismal prognosis. Magnetic resonance imaging (MRI) has shown superior results to other examinations in preoperative assessment, while cisplatin-based chemotherapy is the first-line treatment for OC. However, few previous studies have brought together the two rapidly expanding fields. Here a technique is presented using cisplatin prodrug (Pt-COOH), Fe3+, and natural polyphenols (Gossypol) to construct the nanoparticles (HA@PFG NPs) that have a stable structure, controllable drug release behavior, and high drug loading capacity. The acidic pH values in tumor sites facilitate the release of Fe3+, Pt-COOH, and Gossypol from HA@PFG NPs. Pt-COOH with GSH consumption and cisplatin-basedchemotherapy plus Gossypol with pro-apoptotic effects displays asynergisticeffect forkillingtumorcells. Furthermore, the release of Fe3+ at the tumor sites promotes ferroptosis and enables MRI imaging of OC. Inthe patient-derived tumor xenograft (PDX)model, HA@PFG NPs alleviate the tumor activity. RNA sequencing analysis reveals that HA@PFG NPs ameliorate OC symptoms mainly through IL-6 signal pathways. This work combines MRI imaging with cisplatin-based chemotherapy, which holds great promise for OC diagnosis and synergistic therapy.

Atomically dispersed Zn sites on N-doped carbon boosted transesterification of symmetrical organic carbonates with biomass-derived alcohols

Transesterification of symmetrical organic carbonates with alcohols to access the unsymmetrical ones is a highly attractive strategy for upgrading biomass-derived alcohols. Robust, facile-prepared, and cost-effective catalytic materials remain highly desirable for this route. Herein, we designed several Zn-based catalysts (denoted as Zn@C-T, where T represented the pyrolysis temperature) by the pyrolysis of Zn-based coordination polymer at different temperatures. Very interestingly, the prepared Zn@C-900 could efficiently catalyze the transesterification of diethyl carbonate (DEC) with various biomass-derived alcohols to synthesize the corresponding unsymmetrical organic carbonates with high yields (>95 %), resulting from the atomically dispersed ZnNx sites on the N-doped carbon. Notably, good catalytic activity could be obtained at a low temperature of 80 °C, representing the major breakthrough. Detailed investigations indicated that the excellent performance of Zn@C-900 originated mainly from the synergistic effect of Zn (to activate DEC) and N (to activate the alcohols) in the ZnNx sites. This work provided a promising efficient catalyst for low-temperature production of unsymmetrical organic carbonates via transesterification of DEC.

Isostructural Oxamate Complexes with Visible Luminescence (Eu3+) and Field-Induced Single-Molecule Magnet (Nd3+).

The search for new metal-organic compounds as candidates for quantum information processing technologies is in the spotlight. Several metal ions and organic linkers have been used to obtain such compounds. Herein, we describe the synthesis, crystal structures, and cryomagnetic properties of two air-stable isostructural neodymium(III) and europium(III) one-dimensional (1D) coordination polymers of formula [Nd(Hmpa)3(DMSO)2]n (1) and [Eu(Hmpa)3(DMSO)2]n (2) [Hmpa = N-(4-methylphenyl)oxamate, and DMSO = dimethylsulfoxide]. These complexes were prepared by reacting n-Bu4N(Hmpa) proligand [n-Bu4N+ = tetra-n-butylammonium] and the correspondent LnCl3·6H2O salt (Ln = Nd or Eu) in the open air and mild conditions. The crystal structures of 1 and 2 reveal the Ln3+ ion surrounded by two DMSO molecules and three oxamate ligands, one of them connecting to adjacent mononuclear entities through carboxylate bridges featuring a 1D coordination polymer, while the other two establishing double N-H···O hydrogen bonds among adjacent polymers to give a resultant supramolecular 2D network. Cryomagnetic measurements in the static (dc) and dynamic current (ac) regimes reveal that 1 behaves as a field-induced single-molecule magnet below 8.8 K. A photoluminescence study shows that Hmpa ligands efficiently sensitize the luminescence of Eu3+ complex in the visible region in the solid state at room temperature.

Impact of halogen⋯halogen interaction on the mechanical motion of a 3D Pb(II) coordination polymer of elusive topology.

Herein, we report the synthesis of a Pb(II) based three-dimensional coordination polymer (3D CP), [Pb(DCTP)]n (1) [H2DCTP = 2,5-dichloroterephthalic acid] with an unprecedented topology, which exhibits a photomechanical effect wherein crystals show jumping upon UV irradiation. The Pb(II) CP forms a type II Cl⋯Cl interaction, which weakens further upon UV irradiation to resolve the anisotropic mechanical strain. The work presented here could be a beacon to the nascent field of photoactuating smart materials.

Construction of Co(II), Cu(II), and Zn(II) coordination compounds driven by a pyridine-dicarboxylic acid: Hydrothermal assembly, structural and topological versatility, and catalytic properties

A derivative of pyridine-dicarboxylic acid, 5-(3-carboxyphenyl)picolinic acid (H2cpic), was used as a versatile building block to synthesize a series of five novel coordination compounds under hydrothermal conditions and formulated as {[Cu2(μ-cpic)2(phen)]·H2O}n (1), [Co(μ-cpic)(phen)(H2O)]n (2), [Cu2(μ-cpic)2(2,2′-bipy)(H2O)2]·2H2O (3), {[Cu3(μ-cpic)3(μ-4,4′-bipy)1.5(H2O)3]·2H2O}n (4), and {[Zn2(μ-cpic)2(μ-dpe)0.5(H2O)3]·H2O}n (5). The auxiliary ligands used in the synthesis were 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bipy), 4,4′-bipyridine (4,4′-bipy), and 1,2-di(4-pyridyl)ethylene (dpe). The structures of the compounds 1–5 vary significantly, ranging from a 0D tetramer (3) to 1D metal–organic chains (1, 2, 4, and 5). Furthermore, these compounds were evaluated as heterogeneous catalysts for the Henry reaction, achieving high product yields under optimized conditions. We further investigated various reaction parameters, and substrate scope, and assessed the feasibility of catalyst recycling. This thorough investigation highlights the versatility of H2cpic as a dicarboxylate building block in the formation of functional coordination polymers.

Cu(II)-Organic Coordination Polymer Networks for Persistent Nitric Oxide Release in Tumor Therapy.

Nitric oxide (NO) plays a key role in regulating the immune system by polarizing macrophages toward the proinflammatory M1 phenotype, which is beneficial for cancer immunotherapy. We developed a Cu-organic coordination polymer network to sustainably release NO from endogenous donors. This robust polymer network was constructed through a dual-interaction process: complexation and cross-linking. The carboxylate groups of deprotonated 4-((6-(acryloyloxy)hexyl)oxy)benzoic acid (BA) served as bidentate ligands for the formation of Cu(II) complexes. The acrylate moiety of BA anchored these complexes in the polymer network, forming a cross-linked film. Cu ions within the network catalytically promoted NO release from S-nitrosoglutathione, maintaining this release even after 90 days in a physiological environment. The released NO effectively polarized both resting (M0) and tumor-promoting (M2) macrophages to the M1 phenotype. With their demonstrated physiological stability and sustained NO release performance, BA-Cu films hold potential as anticancer patches capable of continuously promoting antitumoral macrophages.

Dynamic, multi-color, multi-level stimulus-responsive luminescence in a co-crystallized coordination polymer: Modulation of energy transfer by acid-induced ligand protonation and photo-induced radical generation

Stimulus-responsive luminescent materials (SLMs), which can respond to external stimuli by switching their luminescence properties, hold great promise for a variety of applications. Particularly, multi-level SLMs with a logical stimulus sequence and a dynamic, multi-color transition are highly desirable for anti-counterfeiting and information encryption, but an effective design strategy is lacking. Herein, a co-crystallized coordination polymer multi-level SLM [Cd(9-AC)4]·(HAD)2·(9-HAC)2 (9-HAC for anthracene-9-carboxylic acid and AD for acridine) with dual emission centers of coordination unit ([Cd(9-AC)4]2-) and exciplex ([9-HAC/HAD]+) has been successfully constructed by a stepwise solvent process. This SLM possesses a variety of stimulus-responsive properties, including mechanochromic (MC), mechanochromic luminescence (MCL), reversible acidochromic luminescence (ACL), and reversible photochromic luminescence (PCL). Notably, both ACL and PCL properties are achieved by modulating the energy transfer process between the coordination unit and the exciplex, while there is a logical sequence between these two stimulus actions. The acid-induced activation and radical-regulated PCL performance has been exploited in the development of anti-counterfeiting and information encryption applications. This work provides an effective strategy to realize dynamic, multi-color, multi-level stimuli-responsive luminescence by modulating the energy transfer through acid-induced ligand protonation and photo-induced radical generation.