Π-conjugated Ligands Research Articles

Hierarchical conductive metal-organic framework films enabling efficient interfacial mass transfer

Heterogeneous reactions associated with porous solid films are ubiquitous and play an important role in both nature and industrial processes. However, due to the no-slip boundary condition in pressure-driven flows, the interfacial mass transfer between the porous solid surface and the environment is largely limited to slow molecular diffusion, which severely hinders the enhancement of heterogeneous reaction kinetics. Herein, we report a hierarchical-structure-accelerated interfacial dynamic strategy to improve interfacial gas transfer on hierarchical conductive metal-organic framework (c-MOF) films. Hierarchical c-MOF films are synthesized via the in-situ transformation of insulating MOF film precursors using π-conjugated ligands and comprise both a nanoporous shell and hollow inner voids. The introduction of hollow structures in the c-MOF films enables an increase of gas permeability, thus enhancing the motion velocity of gas molecules toward the c-MOF film surface, which is more than 8.0-fold higher than that of bulk-type film. The c-MOF film-based chemiresistive sensor exhibits a faster response towards ammonia than other reported chemiresistive ammonia sensors at room temperature and a response speed 10 times faster than that of the bulk-type film.

The Effect of the Interface Layer on the Electronic Parameters of the Light Emitting Electrochemical Cell (LEC) Device Based on Iridium (III) Complex that Calculated by Different Methods

We report a calculation of the electronic parameters and some optical measurement results of a light-emitting electrochemical cell (LEC), one of the most basic forms of electroluminescent films by modifying 4-(4-methoxy-N-naphthalen-1-ylanilino) benzoic acid (MA) as hole injection layer doped with an emissive layer that is ionic transition metal complex (Ir[dF(CF3)ppy]2(dtbpy))PF6-(Ir-iTMC). The electronic parameters of LEC device were computed using three different methods; Cheung and Cheung’s, Conventional Schottky and Norde, to evaluate the ideality factor (n), the barrier height () and the series resistance (Rs) of the LEC device. The formation on indium tin oxide (ITO) substrate was analyzed by Atomic Force Microscopy (AFM). The HOMO-LUMO energy level and electronic charge distribution of the MA molecule were computed theoretically using Chemissian software. The MA’s HOMO-LUMO energy level is determined to be EHOMO = −5.27 eV and ELUMO = −1.40 eV. The ITO surface has been modified with the Self-Assembled Monolayers (SAM) technique as an interlayer to improve the surface working function by simplifying hole injection from the ITO anode to the Hole Transport Layer (HTL) in the LEC. The Ir- iTMC complexes containing Π-conjugated bridging ligand shown better external quantum efficiency (EQE), reaching to 1.49%. The max luminance values of the bare-LEC and LEC-MA are measured as 145 cd m−2 and 1240 cd m−2, respectively.

Air/liquid interfacial formation process of conductive metal–organic framework nanosheets

The air/liquid interface is a superior platform to create nanosheets of materials by promoting spontaneous two-dimensional growth of components. Metal–organic frameworks (MOFs)—intrinsically porous crystals—with π-conjugated triphenylene-based ligands show high electrical conductivities. Forming nanosheets of such conductive MOFs should enable their use in electronic devices. Although highly conductive MOF nanosheets have been created at the air/liquid interface, direct control of their continuity, morphology, thickness, crystallinity, and orientation directly influencing device performance remains as an issue to be addressed. Here, we present detailed insights into the formation process of electrically conductive MOF nanosheets composed of 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and Ni2+ ions (HITP-Ni-NS) at the air/liquid interface. The morphological and structural features of HITP-Ni-NS strongly depend on the standing time—the time without any external actions involved, but leaving the interface undisturbed after setting the ligand solution onto the metal-ion solution. We find that the fundamental features of HITP-Ni-NS are determined by the standing time with conductivity sensitively influenced by such pre-determined HITP-Ni-NS characteristics. These findings will lead towards the establishment of a rational strategy for creating MOF nanosheets at the air/liquid interface with desired properties, thereby accelerating their use in diverse potential applications.

Efficient blue-light-excitable copper(I) coordination network phosphors for high-performance white LEDs

The blue-light-excitable phosphors play a crucial role in the high-performance white LEDs. Here, we report on two new Cu(I) coordination network materials as yellow-emitting phosphors prepared by suitably expanded π-conjugated triazole ligands. Upon blue-light irradiation, these complexes exhibit efficient solid-state emission and enhanced photostability. Through incorporating the yellow phosphor and a commercial blue-green powder (BaSi2N2O2:Eu2+) with a blue LED chip, the phosphor-converted LED devices display remarkable white emission properties. The experimental results demonstrate that the Cu(I) coordination network materials function as promising blue-light excitable phosphors with great application potential for full-spectrum white LEDs.

3D ZnII-Based coordination polymer: Synthesis, structure and fluorescent sensing property for nitroaromatic compounds

A water-stable ZnII-based coordination polymer (CP) with excellent photophysical behavior, namely [Zn2L(atez)(H2O)2] (compound 1; H3L = 4-(2′,3′-dicarboxylphenoxy); atez = 5-aminotetrazole), was successfully prepared by the solvothermal reaction of Zn ions with a π-conjugated and semi-rigid multicarboxylate ligand H3L in the presence of N-containing linker atez. Compound 1 displays a hierarchically pillared three-dimensional (3D) (3,4,5)-connected (4·62) (42·64) (43·64·83) net which is based on two-dimensional (2D) multicarboxylate- ZnII layers strutted by the atez ligands. Sensing investigations of compound 1 reveal that this material can selectively and sensitively detect nitroaromatic compounds in water suspension through fluorescence quenching effect. In particular, it is worth noting that it shows highly specific detection of nitrobenzene (NB) and 2,4,6-trinitrophenol (TNP) with remarkable quenching constants (KSV = 7.5 × 104 M−1 for NB and KSV = 1.9 × 105 M−1 for TNP) and low limit of detection (LOD = 0.93 μM for NB and LOD = 0.36 μM for TNP). Investigations reveal that the probable mechanisms for such sensing processes are the concurrent presence of fluorescence resonance energy transfer (FRET) as well as photoinduced electron transfer (PET) between the CP and nitroaromatic molecules. This work not only offers an effective route to improve the application of fluorescent CPs but also provide one novel probable fluorescence probe for nitroaromatic compounds.

Energy transfer in metal-exchange binuclear complexes covalently linked by asymmetric ligands.

Nitrogen complexation with π-conjugated ligands is an effective strategy for synthesizing luminescent molecules. The asymmetric bridging ligands L (L1 and L2) have been designed. The terminal chelating sites of the L1 and L2 bridging ligands consisted of 2,2'-bipyridine (bpy) and 1,10-phenanthroline moieties (where L = L1 and L2; L1 = 2-(3-((4-([2,2'-bipyridin]-6-yl)benzyl)oxy)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and L2 = 2-(3-((4-(6-phenyl-[2,2'-bipyridin]-4-yl)benzyl)oxy)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline). The full use of the synthetic strategy of the "complexes as ligands and complexes as metals" was expected to successfully design and synthesize a series of conjugated metal-exchange complexes linked by the asymmetric bridging ligands L1 and L2. These compounds included monometallic complexes Ru(L) and (L)Ru (C1, C2, C7, and C8), homometallic complexes Ru(L)Ru (C3 and C4), and heterometallic complexes Os(L)Ru and Ru(L)Os (C5, C6, C9, and C10) with Ru- or Os-based units. C3-C10 complexes exhibited various degrees of octahedral distortion around the Ru(II) or Os(II) center, which was consistent with the optimized geometry of the coordination complexes based on density functional theory calculation. These complexes exhibited intense spin-allowed ligand-centered transitions with high absorbance at around 288 nm upon absorbing visible light. Notably, all complexes exhibited spin-allowed metal-to-ligand charge transfer absorption of the Ru-based units in the 440-450 nm range. In addition, the heterometallic C5, C6, C9, and C10 complexes showed absorption of the Os-based units in the range of 565-583 nm. The intramolecular energy transfer of C3 and C5 was briefly discussed by comparing the emission intensity of monometallic C1 and C2 to that of binuclear complexes C3 and C5, respectively. The results indicated that the intramolecular energy transfer of the Ru(II)/Os(II) polypyridine complexes proceeded from the Ru(II)- to the Os(II)-based units in the heterometallic C5 and C6 complexes.

Interrogating bioinspired ESIPT/PCET-based Ir(iii)-complexes as organelle-targeted phototherapeutics: a redox-catalysis under hypoxia to evoke synergistic ferroptosis/apoptosis.

Installing proton-coupled electron transfer (PCET) in Ir-complexes is indeed a newly explored phenomenon, offering high quantum efficiency and tunable photophysics; however, the prospects for its application in various fields, including interrogating biological systems, are quite open and exciting. Herein, we developed various organelle-targeted Ir(iii)-complexes by leveraging the photoinduced PCET process to see the opportunities in phototherapeutic application and investigate the underlying mechanisms of action (MOAs). We diversified the ligands' nature and also incorporated a H-bonded benzimidazole-phenol (BIP) moiety with π-conjugated ancillary ligands in Ir(iii) to study the excited-state intramolecular proton transfer (ESIPT) process for tuning dual emission bands and to tempt excited-state PCET. These visible or two-photon-NIR light activatable Ir-catalysts generate reactive hydroxyl radicals (˙OH) and simultaneously oxidize electron donating biomolecules (1,4-dihydronicotinamide adenine dinucleotide or glutathione) to disrupt redox homeostasis, downregulate the GPX4 enzyme, and amplify oxidative stress and lipid peroxide (LPO) accumulation. Our homogeneous photocatalytic platform efficiently triggers organelle dysfunction mediated by a Fenton-like pathway with spatiotemporal control upon illumination to evoke ferroptosis poised with the synergistic action of apoptosis in a hypoxic environment leading to cell death. Ir2 is the most efficient photochemotherapy agent among others, which provided profound cytophototoxicity to 4T1 and MCF-7 cancerous cells and inhibited solid hypoxic tumor growth in vitro and in vivo.

Modular metallotecton for engineering permanently porous frameworks: supernumerary role of ancillary ion.

The formation of robust supramolecular frameworks built from hetero-polytopic metal complexes and interacting with different ancillary ions remains a long-standing and underexplored desire. Herein, the secondary sphere interaction chemistry of [Ru(5-oxido-6-hydroxy-1,10-phenanthroline)a(5,6-dihydroxy-1,10-phenanthroline)(3-a)]-(a-2) (1) (a = 1, 3) coordination ion is reported, where the π-conjugated phenanthroline ligands are functionalized with catecholate groups used as H-bond donors and ligands. The deprotonation of the catechols is found to control the overall charge stoichiometry in 1, acting as a metallotecton to interact with anions of different basicity (Cl- in 1.Cl and Br- in 1.Br) as well as with Li+ cations (in 1.Li+). These interactions lead to the formation of 2D porous honeycomb networks without any significant alteration in the molecular packing. This implies that the self-assembly process is controlled by complementary intermolecular non-covalent interactions making the choice of the ancillary ion insignificant. The robust porous structure of the frameworks is established by uptake of D2O and I2 molecules within the microporous channels. This work demonstrates that supramolecular frameworks appear as flexible candidates for applications in gas sorption, separation and chemical sensing.

U-type π-conjugated phosphorescent ligand sensitized lanthanide metal-organic frameworks for efficient white-light-emitting diodes.

Lanthanide metal-organic framework (Ln-MOF) based phosphors for light-emitting diodes (LEDs) play an important role in the fields of solid-state lighting and display. The rational design of organic antennae to address the drawback of low extinction coefficients of the lanthanide ions is highly desired. In this work, we provide a new design strategy to achieve an energy transfer molecule with a through-space conjugated folded structure, which can strengthen the skeleton rigidity and facilitate triplet state energy transfer. Consequently, one U-type π-conjugated molecule 2,6-bis(3,5-dicarboxylphenoxy) pyridine (H4L) was selected as a light gatherer to sensitize lanthanide ions for the construction of Ln-MOFs [Ln(HL)(H2O)3]n (Eu-MOF and Tb-MOF), which exhibit a long-lived luminescence lifetime (0.88 ms for Eu-MOF and 1.31 ms for Tb-MOF) and high quantum yields (50.87% for Eu-MOF and 85.64% for Tb-MOF). Furthermore, a white LED device with a colour rendering index (89) was fabricated using the mixture of Ln-MOFs with a commercial blue phosphor.

A synergetic model for implementing single-component white-light emission: a case study of zero-dimensional cadmium halides

A serial of 0D (C6H7NX)2CdX4 (X = Cl, Br, I) are developed, and the synergetic controlling of π-conjugated ligands and [CdX4] units enables single-component ultra-broadband white-light emissions of (C6H7NCl)2CdCl4 and (C6H7NBr)2CdBr4.

Asymmetric Push–Pull Type Co(II) Porphyrin for Enhanced Electrocatalytic CO2 Reduction Activity

Molecular electrocatalysts for electrochemical carbon dioxide (CO2) reduction has received more attention both by scientists and engineers, owing to their well-defined structure and tunable electronic property. Metal complexes via coordination with many π-conjugated ligands exhibit the unique electrocatalytic CO2 reduction performance. The symmetric electronic structure of this metal complex may play an important role in the CO2 reduction. In this work, two novel dimethoxy substituted asymmetric and cross-symmetric Co(II) porphyrin (PorCo) have been prepared as the model electrocatalyst for CO2 reduction. Owing to the electron donor effect of methoxy group, the intramolecular charge transfer of these push-pull type molecules facilitates the electron mobility. As electrocatalysts at -0.7 V vs. reversible hydrogen electrode (RHE), asymmetric methoxy-substituted Co(II) porphyrin shows the higher CO2-to-CO Faradaic efficiency (FECO) of ~95 % and turnover frequency (TOF) of 2880 h-1 than those of control materials, due to its push-pull type electronic structure. The density functional theory (DFT) calculation further confirms that methoxy group could ready to decrease to energy level for formation *COOH, leading to high CO2 reduction performance. This work opens a novel path to the design of molecular catalysts for boosting electrocatalytic CO2 reduction.

Slow magnetic relaxation behavior of a {Dy2} complex based on a large π-conjugated bridging ligand

Binuclear lanthanide single molecule magnets (Ln-SMMs) based on large π-conjugated bridging ligands have shown potential in achieving excellent SMM performance. However, their members are still scarce until now. In this work, a novel binuclear Ln-SMM featuring a large π-conjugated bridging ligand, [Dy2(hfac)6(tpphz)]·CH2Cl2 (1), has been prepared. Its two DyIII centers are chelated and bridged by the large π-conjugated tetrapyrido[3,2-a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazine (tpphz) ligand. Three 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac-) ions acting as terminal ligands further complete the square antiprism coordination geometry of each DyIII center. Magnetic measurements revealed that 1 exhibits zero field SMM behavior with a single magnetic relaxation process. The effective energy barrier (Ueff) is 13.79 K. Interestingly, dual relaxation behavior including well-separated slow relaxation (SR) and fast relaxation (FR) processes was further observed when a dc field was applied. It could be ascribed to the different single ion anisotropy of the DyIII centers, as well as a possible contribution of magnetic interactions in the system of 1. The Ueff values for the SR and FR processes are 27.3 and 1.30 K, respectively.

Facile wet-chemical fabrication of bi-functional coordination polymer nanosheets for high-performance energy storage and anti-corrosion engineering

Organic materials are of great interest in various applications owing to their intrinsic designability, molecular controllability, ease of synthesis, and ecological sustainability. In this work, a facile and mild wet-chemical strategy was carried out to construct a conjugated Ni-BTA coordination polymer via the π-d hybridization with 1,2,4,5-benzenetetramine (BTA) as π-conjugated ligands and Ni2+ as metallic centers, which exhibits a unique two-dimensional nanosheet-like structure with available active sites, sufficient electrochemical activity, and multi-electron redox capability. On the one hand, the as-prepared Ni-BTA coordination polymer as electrode material exhibits a rapid, reversible, and efficient energy storage behavior with a large reversible capacity of 198 mA·h·g−1 at 1 A·g−1 and a high-rate capability of 150 mA·h·g−1 at 20 A·g−1 in alkali-ion aqueous electrolyte, which are further demonstrated by the in-situ Raman investigation. On the other hand, the Ni-BTA coordination polymer as anti-corrosion additive was introduced into the epoxy resin to achieve a Ni-BTA epoxy coating, which shows a long-term anti-corrosion performance with a low corrosion rate of 4.62 × 10−6 mm·a−1 and a high corrosion inhibition efficiency of 99.86%, suggesting its great engineering potential as the bi-functional organic material for high-performance energy storage and corrosion protection.

Multistimuli-responsive pyrene-based lanthanide (III)-MOF construction and applied as dual-function fluorescent chemosensors for trace water and vitamins molecules

Three novel isostructural 3D porous metal–organic frameworks (3D MOFs) Ln-TBAPy (Ln = Sm (1), La (2), and Nd (3); H4TBAPy = 1,3,6,8-tetrakis (p-benzoic acid)pyrene) were synthesized, encompassing a π-conjugated organic ligand with a pyrene functionality. In particular, the crystal structure of [Sm3 (TBAPy)2 ((μ2-H2O)2(OH)2]∙(guests) (complex 1) was determined by X-ray single-crystal diffraction and displayed excellent performance in luminescent, which featured the alb topology and remarkable multiple pores dimensions. The complex 1 was utilized to determine the pH-dependent and temperature-dependent fluorescence under multistimuli responses, which exhibits its unusual photophysical characteristics and outstanding stability under special conditions. Markedly, the complex 1 probe achieves ultra-sensitive turn-on detection of trace water in organic solvent dioxane, exhibiting an ultra-low detection limit of 0.005% (v/v). In addition, we have explored that it has excellent fluorescence detection selective effect on various biological small molecule vitamins. On the one hand, the complex 1 can sense Vit-B6 with unique fluorescent switch ‘turn-on-off’ behavior, based on the changing concentration of Vit-B6 in MOF channel and hydrogen bond between host–guest interaction. On the other hand, complex 1 has high sensitivity to the quenching of Vit-B9 and Vit-K3, with the LOD as low as 0.32 μM, and 3.94 μM, respectively. Our synthesis strategy of Ln-TBAPy MOF materials will play simultaneously multiple roles and open up an effective avenue to dual-function fluorescence sensor of water and biological small molecule vitamins.

Vapor sorption behavior in heptazine-based MOF featuring a brick-shaped framework

A new porous MOF, [Mg1.5(HTB)2]·2Me2NH2·3DMF·12MeOH, (1) (HTB ​= ​s-heptazine tribenzoate) was successfully synthesized by employing a π-conjugated organic ligand possessing a brick-shaped framework. The activated 1a was investigated as an adsorbent towards a series of vapors (H2O, MeOH, EtOH, n-PrOH and CH2Cl2). The H2O vapor adsorption capacity of 1a can reach 533.9 ​cm3 ​g−1. Interesting, the absorption isotherm of MeOH shows an obvious stepwise sorption phenomenon with the saturated adsorption capacity of 300.8 ​cm3 ​g−1, whereas the bulker EtOH, n-PrOH and CH2Cl2 present hardly any uptakes. Moreover, the IAST selectivities of equimolar H2O/MeOH and H2O/EtOH vapor mixtures was calculated, GCMC simulations were performed to locate the framework-vapor binding sites.

Rod-shaped units based cobalt(II) organic framework as an efficient electrochemical sensor for uric acid detection in serum

Benefits from the unique [Co3(COO)4(μ3-O)2]n rod-shaped units and aromatic π-conjugated ligand, a 3D cobalt(II) organic framework was selected to explore its potential as a uric acid (UA) electrochemical sensor by coating onto the glassy carbon electrode (GCE). By utilizing electrocatalytic oxidation effects, the prepared modified electrode of 1/CB/GCE shows remarkable electrochemical sensing performances for detecting UA in PBS solution (pH = 7) with high sensitivity, high selectivity, good recyclability, and low detection limit of 3.4 ppb. This work demonstrates MOF-based composite materials have great potentials in clinical medicine, thereby providing a new way to design and develop electrochemical biosensors.

{Mo126 W30 }: Polyoxometalate Cages Shaped by π-π Interactions.

Here we report the formation of giant {Mo126 W30 } polyoxometalate cages templated by π-conjugated planar ligands. Their inorganic shells incorporate arrays of 18 stacked aromatic carboxylates, such as 1,3,5-benzenetricarboxylate or 5-nitroisophthalate, and the assembly is stabilized by multiple π-π interactions. NMR data confirmed that the cages are stable in solution and the inner aromatic templates can be postsynthetically replaced by selected aliphatic dicarboxylates, paving the way for endo-functionalization and exploration of the reactivities within the cage cavities.

Extended π-Conjugated Ligands Tune Excited-State Energies of Iron(II) Polypyridine Dyes

Over the past decade, iron(II) polypyridines have gained a lot of attention as potential chromophores and sensitizers due to the low cost and high abundance of iron. Unfortunately, most iron(II) polypyridines are poor chromophores since their initially excited, photoactive metal-to-ligand charge transfer (MLCT) states quickly decay into non-photoactive metal-centered (MC) states. Many strategies to increase their lifetime have been pursued, built mainly around increasing the ligand field strength of these complexes and thus destabilizing the MC states. In this work, we aim to design a new class of Fe(II) complexes by stabilizing the energies of their MLCT states. To this end, we employ density functional theory (DFT) and time-dependent DFT to investigate a series of Fe(II) complexes, [Fe(L/X)2,4(N^N)]2+/2- where L/X represents either cyanide, isocyanide, or bipyridine ligands and N̂N stands for bidentate-extended π-conjugated ligands derived from the bipyridine. The L/X ligands tune the energetics of the Fe-based t2g molecular orbitals, while the amount of π-conjugation on the N^N ligand impacts the energies of its π and π* orbitals, thus tuning the energetics of the MLCT and the ligand-centered (LC) states. Overall, our results suggest that the use of N^N ligands with the extended π-conjugation is a viable strategy to tune the relative energies of MLCT, LC, and MC states.

The [CuI4Cl4] cluster of a coordination complex based on polypyridyl ligand for heterogeneous Fenton-like MB degradation without illumination and electrocatalytic reduction of H2O2 and K2Cr2O7

Developing novel materials for elimination of organic pollutants in wastewater has become one of the most imperious demands for human environment. Herein, a [CuI4Cl4]-containing complex [Cu4(DNP)Cl4)] (1) (DNP = 2,6-di(1,8-naphthyridine-2-yl)pyridine) based on π-conjugated polypyridyl ligand has been solvothermally synthesized, exhibiting a three-dimensional structure via C–H⋯Cl hydrogen bonds and π···π interactions between pyridine rings. Complex 1 displays good Fenton-like degradation efficiency toward methylene blue (MB) with the rate of 71.9% in 120 min under dark condition, in which the interactions between CuI centers and DNP are of extraordinary importance for enhanced degradation efficiency. The degradation products are identified by liquid chromatography-mass spectrometry (LC-MS) and two MB degradation pathways have been proposed. In addition, complex 1 demonstrates good electrocatalytic activity for reduction of H2O2 and K2Cr2O7 via redox of CuII/CuI. This work presents an effective strategy for the rational design of coordination complexes for Fenton-like catalysis and electrocatalytic reduction.

Selective and Multicyclic CO2 Adsorption with Visible Light-Driven Photodegradation of Organic Dyes in a Robust Metal-Organic Framework Embracing Heteroatom-Affixed Pores.

Pore environment modulation with polarizing groups is one of the essential prerequisites for selective carbon dioxide (CO2) adsorption in metal-organic frameworks (MOFs), wherein judicious installation of the photocatalytic feature can promise visible light-triggered degradation of toxic organic dye molecules. However, astute amalgamation of both these attributes over a single MOF is rather rare, yet much anticipated in view of sustainable applications. Pore engineering is effectively harnessed in a Zn(II)-based three-dimensional (3D) MOF, CSMCRI-16 (CSMCRI = Central Salt and Marine Chemicals Research Institute), through mixed-ligand assembly of a N-rich linker (L), 4,4'-oxybis(benzoic acid) (H2oba) ligand, and [Zn2(CO2)4N2] paddle-wheel secondary building units (SBUs). The noninterpenetrated structure contains unbound nitrogen and accessible oxygen atom-decorated porous channels and exhibits admirable stability in diverse organic solvents, open air, and at elevated temperatures. The heteroatom-decorated porous channels facilitated excellent CO2 uptake in the activated MOF (16a) with high selectivity over N2 (CO2/N2: 155.3) at 273 K. The framework further exhibits reasonable CO2 affinity and multicyclic CO2 sorption recurrence without a significant loss in the uptake capacity. Benefitting from the presence of the [Zn2(CO2)4N2] cluster in conjugation with π-conjugated organic ligands, the extended 3D network revealed an optical band gap energy of 2.55 eV, which makes the MOF an efficient photocatalyst toward the degradation of the cationic dyes crystal violet (CV) and methylene blue (MB) in the presence of a simple 40 W visible light lamp without any assistance of external oxidants. The catalyst exhibits multicyclic performance and short reaction time in addition to the fact that catalytic efficiencies (CV: 97.2%, MB: 97.8%) are comparable to those of contemporary materials.