Two-dimensional Metal-organic Framework Research Articles

Mechanical Properties of Modulative Undulating Layers in Two-Dimensional Metal–Organic Frameworks

Mechanical Properties of Modulative Undulating Layers in Two-Dimensional Metal–Organic Frameworks

Dimensional Reduction of Metal-Organic Frameworks for Photocatalytic Synthesis of Fused Tetracyclic Heterocycles.

Heterogeneous palladium catalysts with high efficiency, high Pd atom utilization, simplified separation, and recycle have attracted considerable attention in the field of synthetic chemistry. Herein, we reported a zirconium-based two-dimensional metal-organic framework (2D-MOF)-based Pd(II) photocatalyst (Zr-Ir-Pd) by merging the Ir photosensitizers and Pd(II) species into the skeletons of the 2D-MOF for the Pd(II)-catalyzed oxidation reaction. Morphological and structural characterization identified that Zr-Ir-Pd with a specific nanoflower-like structure consists of ultrathin 2D-MOF nanosheets (3.85 nm). Due to its excellent visible-light response and absorption capability, faster transfer and separation of photogenerated carriers, more accessible Pd active sites, and low mass transfer resistance, Zr-Ir-Pd exhibited boosted photocatalytic activity in catalyzing sterically hindered isocyanide insertion of diarylalkynes for the construction of fused tetracyclic heterocycles, with up to 12 times the Pd catalyst turnover number than the existing catalytic systems. In addition, Zr-Ir-Pd inhibited the competitive agglomeration of Pd(0) species and could be reused at least five times, owing to the stabilization of 2D-MOF on the single-site Pd and Ir sites. Finally, a possible mechanism of the photocatalytic synthesis of fused tetracyclic heterocycles catalyzed by Zr-Ir-Pd was proposed.

Benchmark Investigation of SCC-DFTB against Standard and Hybrid DFT to Model Electronic Properties in Two-Dimensional MOFs for Thermoelectric Applications.

Recent studies have shown that metal-organic frameworks (MOFs) have potential as thermoelectric materials, and the topic has received increasing attention. The main motivation for this project is to further our knowledge of thermoelectric properties in MOFs and find which available self-consistent-charge density functional tight binding (SCC-DFTB) method can best predict (at least trends in) the electronic properties of MOFs at a lower computational cost than standard density functional theory (DFT). In this work, the electronic properties of monolayer, serrated, AA-stacked, and/or AB-stacked Zn3C6O6, Cd3C6O6, Zn-NH-MOF─for which no previous calculations of thermoelectric performance exist─and Ni3(HITP)2 MOFs are modeled with DFT-PBE, DFT-HSE06, GFN1-xTB, GFN2-xTB, and DFTB-3ob/mio. The band structures, density of states, and their relative orbital contributions, as well as the electrical conductivity, Seebeck coefficient, and power factor, are compared across methods and geometries. Our results suggest that GFN-xTB is adequate to predict the MOFs' band structure shape and density of states but not band gap. Our calculations further indicate that Zn3C6O6, Cd3C6O6, and Zn-NH-MOF have higher power factor values than Ni3(HITP)2, one of the highest performing synthesized MOFs, and are therefore promising for thermoelectric applications.

Two-dimensional metal–organic framework for post-synthetic immobilization of graphene quantum dots for photoluminescent sensing

Immobilization of graphene quantum dots (GQDs) on a solid support is crucial to prevent GQDs from aggregation in the form of solid powder and facilitate the separation and recycling of GQDs after use. Herein, spatially dispersed GQDs are post-synthetically coordinated within a two-dimensional (2D) and water-stable zirconium-based metal–organic framework (MOF). Unlike pristine GQDs, the obtained GQDs immobilized on 2D MOF sheets show photoluminescence in both suspension and dry powder. Chemical and photoluminescent stabilities of MOF-immobilized GQDs in water are investigated, and the use of immobilized GQDs in the photoluminescent detection of copper ions is demonstrated. Findings here shed the light on the use of 2D MOFs as a platform to further immobilize GQDs with various sizes and distinct chemical functionalities for a range of applications.

Metal-organic frameworks as an active substrate for cell-interaction studies and cell-on-a-chip platforms

Metal-organic frameworks (MOFs) are an emerging class of materials with immense biomedical potential for their unique interactions with biological and organic materials. In this work, we select two candidate two-dimensional (2D) MOF systems based on Fe3+ and Ni2+ metal centers and 2-aminoterephthalate acid ligand (Fe-MOF and Ni-MOF) and evaluate their performance as an active interface for study of cell-interactions. 2D Fe-MOF and Ni-MOF were synthesized onto hydroxyl-modified gold and glass substrates using a layer-by-layer liquid-phase-epitaxy (LbL-LPE) growth at room temperature and used as active substrates (Fe-MOF/glass, Fe-MOF/Au, Ni-MOF/glass and Ni-MOF/Au, respectively) for MTT cell-proliferation and reactive oxygen species tests using the PC-12 cell-line in order to investigate the biocompatibility. Immunostaining and morphological analyses of PC-12 cells on MOF interfaces suggested a stronger cell-substrate interaction in comparison to glass and were further characterized using the Electrical Cell-substrate Impedance Sensing (ECIS) technique, here for the first time, employed to study cell attachment, spreading and proliferation on 2D Fe-MOF. The 2D Fe-MOF showed superior long-term stability in cell culture medium by recording impedance over 24 hours, crucial to monitor cell-dynamics at a solid-liquid interface. A significant increase of interfacial impedance was observed in ECIS, due to PC-12 cells adhering onto 2D Fe-MOF, which was also confirmed by the focused ion beam etching followed by scanning electron microscopy. Our novel findings, therefore, suggest 2D MOFs as highly suitable platform for the study of cell-related interactions using electrical techniques and potentially pave the way for future use of MOFs for bioelectronics and biosensor applications.

In-situ electrochemical activation of a nickel metal-organic framework modified TiO2 photoanode for urea photoelectrocatalysis

Metal-organic frameworks (MOFs) possess a large specific surface area, porosity, and structural diversity, making them ideal candidates for catalysing the urea oxidation reaction (UOR). Even though MOF-based catalysts have been broadly investigated in urea electrocatalysis, few MOF catalysts are used for urea photoelectrocatalysis. The latter requires the MOF-based catalysts to efficiently separate and transport the photogenerated holes at the interface of photoanode-electrolyte junctions. In this study, a sulphur-containing organic ligand of 1,4-benzenedithiol (BDT) is innovatively employed to synthesize two-dimensional Ni-BDT MOFs from Ni(OH)2 nanosheets precursor. After the in-situ electrochemical activation of TiO2@Ni-BDT, the resultant MOF derivative modified TiO2 photoanode named as TiO2@Ni-BDT-A exhibits 3.83 times photocurrent in comparison with the pristine TiO2. A high photovoltage of 0.73 V and an impressive 82 % photocurrent retention after a long-term stability test can also be observed. The improvements are attributed to the enhanced surface active sites and the active species of Ni(2−σ)+−SOx, which can efficiently promote charge separation, increase conductivity, improve donor concentration, and lower the charge transfer resistance. This work develops a sulphur-containing Ni-MOF as a co-catalyst for efficient urea photoelectrocatalysis, and an effective strategy of in-situ electrochemical activation to boost photoanode activity.

Copper-Based Two-Dimensional Metal-Organic Frameworks for Fenton-like Photocatalytic Degradation of Methylene Blue under UV and Sunlight Irradiation.

To efficiently degrade organic pollutants, photocatalysts must be effective under both ultraviolet (UV) radiation and sunlight. We synthesized a series of new metal-organic frameworks by using mild hydrothermal conditions. These frameworks incorporate three distinct bipyridyl ligands: pyrazine (pyr), 4,4'-bipyridine (bpy), and 1,2-bis(4-pyridyl)ethane (bpe). The resulting compounds are denoted as [Cu(pyz)(H2O)2MF6], [Cu(bpy)2(H2O)2]·MF6, and [Cu(bpe)2(H2O)2]·MF6·H2O [M = Zr (1, 3, and 5) and Hf (2, 4, and 6)]. All six compounds exhibited a two-dimensional crystal structure comprising infinitely nonintersecting linear chains. Compound 3 achieved 100% degradation of methylene blue (MB) after 8 min under UV irradiation and 100 min under natural sunlight in the presence of H2O2 as the electron acceptor. For compound 5, 100% MB degradation was achieved after 120 min under sunlight and 10 min under UV light. Moreover, reactive radical tests revealed that the dominant species involved in photocatalytic degradation are hydroxyl (•OH), superoxide radicals (•O2-), and photogenerated holes (h+). The photodegradation process followed pseudo-first-order kinetics, with photodegradation rate constants of 0.362 min-1 (0.039 min-1) for 3 and 0.316 min-1 (0.033 min-1) for 5 under UV (sunlight) irradiation. The developed photocatalysts with excellent activity and good recyclability are promising green catalysts for degrading organic pollutants during environmental decontamination.

Self-condensation-assisted chemical vapour deposition growth of atomically two-dimensional MOF single-crystals

Two-dimensional metal-organic frameworks (MOFs) have a wide variety of applications in molecular separation and other emerging technologies, including atomically thin electronics. However, due to the inherent fragility and strong interlayer interactions, high-quality MOF crystals of atomic thickness, especially isolated MOF crystal monolayers, have not been easy to prepare. Here, we report the self-condensation-assisted chemical vapour deposition growth of atomically thin MOF single-crystals, yielding monolayer single-crystals of poly[Fe(benzimidazole)2] up to 62 μm in grain sizes. By using transmission electron microscopy and high-resolution atomic force microscopy, high crystallinity and atomic-scale single-crystal structure are verified in the atomically MOF flakes. Moreover, integrating such MOFs with MoS2 to construct ultrathin van der Waals heterostructures is achieved by direct growth of atomically MOF single-crystals onto monolayer MoS2, and enables a highly selective ammonia sensing. These demonstrations signify the great potential of the method in facilitating the development of the fabrication and application of atomically thin MOF crystals.

Two-Dimensional Conjugated Metal-Organic Frameworks with a Ring-in-Ring Topology and High Electrical Conductance.

Electrically conducting two-dimensional (2D) metal-organic frameworks (MOFs) have garnered significant interest due to their remarkable structural tunability and outstanding electrical properties. However, the design and synthesis of high-performance materials face challenges due to the limited availability of specific ligands and pore structures. In this study, we have employed a novel highly branched D3h symmetrical planar conjugated ligand, dodechydroxylhexabenzotrinaphthylene (DHHBTN) to fabricate a series of 2D conductive MOFs, named M-DHHBTN (M = Co, Ni, and Cu). This new family of MOFs offers two distinct types of pores, elevating the structural complexity of 2D conductive MOFs to a more advanced level. The intricate tessellation patterns of the M-DHHBTN are elucidated through comprehensive analyses involving powder X-ray diffraction, theoretical simulations, and high-resolution transmission electron microscope. Optical-pump terahertz-probe spectroscopic measurements unveiled carrier mobility in DHHBTN-based 2D MOFs spanning from 0.69 to 3.10 cm2 V-1 s-1. Among M-DHHBTN famility, Cu-DHHBTN displayed high electrical conductivity reaching 0.21 S cm-1 at 298 K with thermal activation behavior. This work leverages the "branched conjugation" of the ligand to encode heteroporosity into highly conductive 2D MOFs, underscoring the significant potential of heterogeneous double-pore structures for future applications.

Phthalocyanine and Porphyrin Derivatives and Their Hybrid Materials in Optical Sensors Based on the Phenomenon of Surface Plasmon Resonance

In this review, the state of research over the past fifteen years in the field of the applications of metal phthalocyanines and porphyrin derivatives as well as their hybrid materials with carbon nanotubes, metal oxides, and polymers in optical sensors based on the phenomenon of surface plasmon resonance (SPR) is analyzed. The first chapter of the review presents an analysis of works on the use of porphyrins and phthalocyanines in classical SPR sensors for the detection of gases and volatile organic vapors, as well as their improved modifications, such as total internal reflection ellipsometry (TIRE) and magneto-optical SPR (MOSPR) methods, while the second chapter is devoted to their application for the detection of various analytes in solutions. The third chapter of the review summarizes publications describing recent advances in the use of porous materials based on hybrids of carbon nanotubes and oxides with metal phthalocyanines. The fourth chapter describes two-dimensional metal-organic frameworks (MOFs) based on metal porphyrin derivatives as SPR sensitizers.

Two-dimensional metal-organic framework nanozyme-mediated portable paper-based analytical device for dichlorophen assay

The metal-organic frameworks (MOFs) nanozyme-mediated paper-based analytical devices (PADs) have shown great potential in portable visual determination of phenolic compounds in the environment. However, most MOF nanozymes suffer from poor dispersibility and block-like structure, which often prompts deposition and results in diminished enzymatic activity, severely hindering their environmental applications. Here, we proposed colorimetric PADs for the visual detection of dichlorophen (Dcp) based on its significant inhibitory effect on the two-dimensional (2D) MOF nanozyme activity. Specifically, we synthesized a 2D Cu TCPP (Fe) (defined as 2D-CTF) MOF nanozyme exhibiting excellent dispersibility and remarkable peroxidase-like (POD-like) activity, which could catalyze the oxidation and subsequent color change of 3,3′,5,5′-tetramethylbenzidine even under neutral conditions. Notably, the POD-like activity of 2D-CTF demonstrated a unique response to Dcp because of the occupation of Fe–N4 active sites on the 2D-CTF. This property enables the use of 2D-CTF as a highly efficient catalyst to develop colorimetric PADs for naked-eye and portable detection of Dcp. We believe that the proposed colorimetric PADs offer an efficient method for Dcp assay and open fresh avenues for the advancement of colorimetric sensors for analyzing of phenolic toxic substances in real samples.

Thermodynamically and Kinetically Enhanced Benzene Vapor Sensor Based on the Cu-TCPP-Cu MOF with Extremely Low Limit of Detection.

As a carcinogenic and highly neurotoxic hazardous gas, benzene vapor is particularly difficult to be distinguished in BTEX (benzene, toluene, ethylbenzene, xylene) atmosphere and be detected in low concentrations due to its chemical inertness. Herein, we develop a depth-related pore structure in Cu-TCPP-Cu to thermodynamically and kinetically enhance the adsorption of benzene vapor and realize the detection of ultralow-temperature benzene gas. We find that the in-plane π electronic nature and proper pore sizes in Cu-TCPP-Cu can selectively induce the adsorption and diffusion of BTEX. Interestingly, the theoretical calculations (including density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations) exhibit that benzene molecules are preferred to adsorb and array as a consecutive arrangement mode in the Cu-TCPP-Cu pore, while the TEX (toluene, ethylbenzene, xylene) dominate the jumping arrangement model. The differences in distribution behaviors can allow adsorption and diffusion of more benzene molecules within limited room. Furthermore, the optimal pore-depth range (60-65 nm) of Cu-TCPP-Cu allows more exposure of active sites and hinders the gas-blocking process. The optimized sensor exhibits ultrahigh sensitivity to benzene vapor (155 Hz/μg@1 ppm), fast response time (less than 10 s), extremely low limit of detection (65 ppb), and excellent selectivity (83%). Our research thus provides a fundamental understanding to design and optimize two-dimensional metal-organic framework (MOF)-based gas sensors.

Expression of Concern: In-Silico Tuning of the Nano-Bio Interface by Molecular Dynamics Method: Amyloid beta Targeting with Two-Dimensional Metal-organic Frameworks

Expression of Concern: In-Silico Tuning of the Nano-Bio Interface by Molecular Dynamics Method: Amyloid beta Targeting with Two-Dimensional Metal-organic Frameworks

Coordination Self-Assembled AuTPyP-Cu Metal-Organic Framework Nanosheets with pH/Ultrasound Dual-Responsiveness for Synergistically Triggering Cuproptosis-Augmented Chemotherapy.

Reactive oxygen species (ROS) mediated tumor cell death is a powerful anticancer strategy. Cuproptosis is a copper-dependent and ROS-mediated prospective tumor therapy strategy. However, the complex tumor microenvironment (TME), low tumor specificity, poor therapy efficiency, and lack of imaging capability impair the therapy output of current cuproptosis drugs. Herein, we designed a dual-responsive two-dimensional metal-organic framework (2D MOF) nanotheranostic via a coordination self-assembly strategy using Au(III) tetra-(4-pyridyl) porphine (AuTPyP) as the ligand and copper ions (Cu2+) as nodes. The dual-stimulus combined with the protonation of the pyridyl group in AuTPyP and deep-penetration ultrasound (US) together triggered the controlled release in an acidic TME. The ultrathin structure (3.0 nm) of nanotheranostics promoted the release process. The released Cu2+ was reduced to Cu+ by depleting the overexpressed glutathione (GSH) in the tumor, which not only activated the Ferredoxin 1 (FDX1)-mediated cuproptosis but also catalyzed the overexpressed hydrogen peroxide (H2O2) in the tumor into reactive oxygen species via Fenton-like reaction. Simultaneously, the released AuTPyP could specifically bind with thioredoxin reductase and activate the redox imbalance of tumor cells. These together selectively induced significant mitochondrial vacuoles and prominent tumor cell death but did not damage the normal cells. The fluorescence and magnetic resonance imaging (MRI) results verified this nanotheranostic could target the HeLa tumor to greatly promote the self-enhanced effect of chemotherapy/cuproptosis and tumor inhibition efficiency. The work helped to elucidate the controlled assembly of multiresponsive nanotheranostics and the high-specificity ROS regulation for application in anticancer therapy.

Light-responsive and ultrapermeable two-dimensional metal-organic framework membrane for efficient ionic energy harvesting

Nanofluidic membranes offer exceptional promise for osmotic energy conversion, but the challenge of balancing ionic selectivity and permeability persists. Here, we present a bionic nanofluidic system based on two-dimensional (2D) copper tetra-(4-carboxyphenyl) porphyrin framework (Cu-TCPP). The inherent nanoporous structure and horizontal interlayer channels endow the Cu-TCPP membrane with ultrahigh ion permeability and allow for a power density of 16.64 W m−2, surpassing state of-the-art nanochannel membranes. Moreover, leveraging the photo-thermal property of Cu-TCPP, light-controlled ion active transport is realized even under natural sunlight. By combining solar energy with salinity gradient, the driving force for ion transport is reinforced, leading to further improvements in energy conversion performance. Notably, light could even eliminate the need for salinity gradient, achieving a power density of 0.82 W m−2 in a symmetric solution system. Our work introduces a new perspective on developing advanced membranes for solar/ionic energy conversion and extends the concept of salinity energy to a notion of ionic energy.

Liquid-Liquid interfacial approach for rapid synthesis of Well-Crystalline Two-Dimensional Metal-Organic frameworks for nitro reduction

Two-dimensional metal–organic frameworks (2D MOFs) have garnered significant attention due to their exceptional properties across diverse research domains, including catalysis, biomedicine, gas adsorption, separation, energy storage, and sensing. Despite these promising attributes, the facile and large-scale synthesis of 2D MOFs with high crystallinity remains a formidable challenge. In this study, we propose a novel approach based on a modified liquid–liquid interfacial method for the rapid synthesis of well-crystalline 2D MOFs. By vigorously mixing water, a hydrophobic solvent, and an emulsifier, we generate micrometer-sized droplets that create substantial curved two-phase interfaces. This method is compatible with various ligands and metal ions, enabling the rapid formation of 2D MOFs at these curved interfaces under additional pressure. The subsequent separation of oil and water phases via centrifugal force promotes moderate π-π stacking within the 2D MOF, thereby stabilizing the lamellar structure and enriching the material at the two-phase interface. Remarkably, the entire synthesis process requires a mere 3 min, yielding grams of product in a single run. Furthermore, solvent reuse does not compromise the quality of the resulting 2D MOFs. As a practical application, we synthesized phthalocyanine (Pc)-based structures using this method for the catalytic reduction of nitroaromatics. Among these, Cu-CoPc (2D MOFs with Cu2+ coordinated to CoPc) emerged as the most active catalyst, achieving a turnover frequency (TOF) value of 4726 h−1 for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). Notably, this TOF value surpasses that of non-precious catalysts and is 180 times higher than that of commercial Pd/C (10 wt%).

2D MOF-enhanced SPR detector based on tunable supramolecular probes for direct and sensitive detection of DOX in serum.

Therapeutic drug monitoring of doxorubicin (DOX) is important to studypharmacokinetics in patients undergoing chemotherapy for reduction ofside effects and improve patient survival by rationally controlling the dose of DOX. A fast and ultra-sensitive surface plasmon resonance (SPR) detector without sample pre-handling was developed for DOX monitoring. First, the two-dimensional metal-organic framework was modified on the Au film to enhance SPR, and then, the supramolecular probes with tunable cavity structure were self-assembled at the sensing interface for direct detection of DOX through specific host-guest interactions with a low detection limit of 60.24pM. The precise monitoring of DOX in serum proved the possibility of clinical application with recoveries in the range 102.86-109.47%. The mechanisms of host-guest interactions between supramolecular and small-molecule drugs were explored in depth through first-principles calculations combined with SPR experiments. The study paves the way for designing facile and sensitive detectors and provides theoretical support and a new methodology for the specific detection of small molecules through calixarene cavity modulation.

In Situ Exfoliation Growth Strategy Realizing Controlled Synthesis of 3D to 2D MOF Materials as High-Performance Electrochemical Biosensors.

Two-dimensional (2D) metal-organic framework (MOF) nanosheets with large surface area, ultrathin thickness, and highly accessible active sites have attracted great research attention. Developing efficient approaches to realize the controllable synthesis of well-defined 2D MOFs with a specific composition and morphology is critical. However, it is still a significant challenge to construct thin and uniform 2D MOF nanosheets and resolve the reagglomeration as well as poor stability of target 2D MOF products. Here, an "in situ exfoliation growth" strategy is proposed, where a one-step synthetic process can realize the successful fabrication of PBA/MIL-53(NiFe)/NF nanosheets on the surface of nickel foam (NF) via in situ conversion and exfoliation growth strategies. The PBA/MIL-53(NiFe)/NF nanosheets combine the individual advantages of MOFs, Prussian blue analogues (PBAs), and 2D materials. As expected, the resulting PBA/MIL-53(NiFe)/NF as a glucose electrode exhibits an extremely high sensitivity of 25.74 mA mM-1 cm-2 in a very wide concentration range of 180 nM to 4.8 μM. The present exciting work provides a simple and effective strategy for the construction of high-performance nonenzymatic glucose electrochemical biosensors.

Bifunctional two-dimensional copper-organic framework for high catalytic performance on cycloaddition of CO2 with epoxides and deacetalization-Knoevenagel condensation

Due to the larger external surface areas and more accessible active sites, two-dimensional (2D) metal-organic frameworks (MOFs) have aroused great interest in the catalytic field. Herein, the exquisite combination of Cu2+ and designed flexible tetracarboxylic acid of 1,1′-(1,3-phenylenebis(methylene))bis(1H-benzo[d]imidazole-5,6-dicarboxylic acid) (H4PBDA) under the solvothermal condition offers a highly robust 2D network of [Cu(H2PBDA)(H2O)]n (NUC-130), which are interlaced via hydrogen-bonding interactions to form a 3D skeleton. After removing associated solvent molecules by activation, NUC-130a is a scarcely reported Lewis acid/Brönsted acid mediated host framework, which can serve as a promising multifunctional catalyst due to the plentiful active sites including exposed penta-coordinated Cu2+ ions, Brønsted acidic sites of -COOH, and Lewis basic sites of Nbenzimidazole atoms and C=O groups. Performed experiments confirmed that NUC-130a had the high catalytic performance on the cycloaddition of CO2 with a series of epoxide derivatives under solvent-free mild conditions. Furthermore, for deacetalization-Knoevenagel condensation based on acid-base catalysis, NUC-130a also shows excellent catalytic activity, which should be ascribed to that dimethyl acetal can be more effectively hydrolyzed by free -COOH group into formyl group than simple Lewis acidic metal sites. Hence, this work not only provides a type of promising catalyst for efficient chemical fixation of CO2 and deacetalization-Knoevenagel condensation, but also opens up an avenue to creating multifunctional MOFs with integrating multiple active sites and larger external surface areas.

Intertwining of Localized (d) and Delocalized (π) Spins in Magnetically Frustrated Two-Dimensional Metal-Organic Frameworks.

Two-dimensional metal-organic frameworks (2D MOFs) are emerging as a new class of multifunctional materials for diversified applications, although magnetic properties have not been widely explored. The metal ions and organic ligands in some of the 2D MOFs are arranged in the well-known Kagome lattice, leading to geometric spin frustration. Hence, such systems could be the potential candidates to exhibit an exotic quantum spin liquid (QSL) state, as was observed in Cu3(HHTP)2 (HHTP = hexahydroxytriphenylene), with no magnetic transition down to 38 mK. Hereto, we have investigated the spin intertwining in a bimetallic 2D MOF system, M3(HHTP)2 (M = Cu/Zn), arising from the localized (d-electron) and delocalized (π-electron) S = 1/2 spins from the Cu(II) ions and the HHTP radicals, respectively. The origin of the spin frustration (down to 5K) was critically examined by varying the metal composition in bimetallic systems, CuxZn3-x(HHTP)2 (x = 1, 1.5, 2), containing both S = 1/2 and S = 0 spins. Additionally, to gain a deeper understanding, we studied the spin interaction in the pristine Zn3(HHTP)2 system containing only S = 0 Zn(II) ions. In view of the quantitative estimate of the localized and delocalized spins, the d-π spin correlation appears essential in understanding the unusual magnetic and/or other physical properties of such hybrid organic-inorganic 2D crystalline solids.