Metal-organic Networks Research Articles

Effect of the flexible chain length of a dimetal subunit on the formation of 1D coordination polymers to molecular rectangles.

Utilizing the angular and rigid furan dicarboxylate (fdc2-) ion, a new series of four (1-4) metal-organic coordination networks (MOCNs) is synthesized in good yields through a one-pot self-assembly reaction in methanol under ambient conditions to demonstrate the effect of Cu2 dimetal subunits, connected by flexible polypyridyl bis(tridentate) ancillary ligands, tpxn, where x refers to the number of methylene groups connecting the alkyl nitrogen atoms in the ancillary ligands and is equal to 2, 4, 6, and 7. The solid-state molecular structures of 1-4 are determined by single-crystal X-ray diffraction. A change in the dimensionality of the resultant MOCN is observed from a 1D coordination polymer (CP) for 1, 2, and 3 to a molecular rectangle for 4. Furthermore, each unit of 4 contains one NaClO4. Using electrospray ionization (ESI) mass spectrometry, their structural integrity in solution and their purity of existence as a single product are confirmed. Further characterization of 1-4 by FTIR and UV-vis (in solution and solid-state) spectroscopy, and FESEM and TEM is also reported. The presence of unsaturated metal centers in 1-4 provided an opportunity to compare their Lewis acid catalytic activities for the Knoevenagel condensation reaction of malononitrile with various aldehydes.

Studies of Metal Organic Networks via M‐Polynomial‐Based Topological Indices

Topological index (TI) is a graph‐theoretic tool that is used to study different physical and structural properties of the networks in various disciplines of science such as computer science, chemistry, and information technology. In this article, we study transition metal tetra‐cyano‐benzene organic networks by computing their M‐polynomials and various topological indices (TIs). At the end, a comparison is also included between all the computed degree‐based topological indices to show their betterness.

Metalloligand-based coordination polymer embedding the nitrosyl ruthenium complex for photoactive materials with bound nitric oxide.

The stability of a photoactivated isonitrosyl state was boosted by confining a pre-designed bicarboxylate ligand with a ruthenium nitrosyl fragment in a 2D metal-organic framework. The novel Zn/Ru-based MOF, {Zn[RuNO(H2O)(inic)2(OH)2]2}·12H2O (inic = isonicotinate), was obtained with enhanced isonitrosyl stability by 30 K (up to 200 K) compared to the related ruthenium-only complex.

Steel-alloy surface protection against saline attacks via the development of Zn(II)-metal-organic networks using Lemon verbena leaves extract (LVLE); Integrated surface/electrochemical explorations

One way to reduce the steel dissolution/corrosion rate in saline (NaCl) media and increase its anti-corrosion durability is by introducing green inhibitors (plant sources). Also, the anti-corrosion performance of the green inhibitors in saline media is not good lonely. Adding metal cations such as Ce and Zinc would be helpful for reaching high anti-corrosion efficiency. In this study, the synergistic effect of Lemon verbena leaves extract (LVLE):Zn cations on the mild steel (MS) corrosion in NaCl electrolyte was explored by electrochemical and morphological methods (i.e. EIS and DC-polarization). The samples' surface microstructure was surveyed by FE-SEM, AFM, GIXRD, and EDS techniques. The results of FE-SEM and AFM displayed that the intact protective layer was formed over the MS surface in the case of applying 200–600 ppm LVLE: Zn over MS surface. The outcomes of electrochemical methods illustrated that the anti-corrosion performance of MS in 3.5% saline solution was improved where the total resistance raised to 37,600 Ω.cm 2 after 24 h of immersion (the inhibition efficiency and synergistic index were about 95% and 50%, respectively) via controlling both anodic and cathodic reactions. The FT-IR spectra and UV-Vis results showed the prosperous interaction between the LVLE and Zn after combination. In addition, the Raman test results displayed the presence of both D and G bands after adsorption of LVLE:Zn complexes on the metal surface. • The Lemon verbena leaves extract (LVLE):Zn hybrid inhibitor anti-corrosion ability on MS surface was explored. • Electrochemical assessments showed excellent LVLE: Zn combination corrosion mitigation performance. • Raman test results displayed the presence of both D and G bands after adsorption of 200–600 ppm LVLE:Zn.

Comparing Cyanophenyl and Pyridyl Ligands in the Formation of Porphyrin-Based Metal-Organic Coordination Networks.

In recent studies, porphyrin derivatives have been frequently used as building blocks for the fabrication of metal–organic coordination networks (MOCNs) on metal surfaces under ultrahigh vacuum conditions (UHV). The porphyrin core can host a variety of 3d transition metals, which are usually incorporated in solution. However, the replacement of a pre-existing metal atom in the porphyrin core by a different metallic species has been rarely reported under UHV. Herein, we studied the influence of cyanophenyl and pyridyl functional endgroups in the self-assembly of structurally different porphyrin-based MOCNs by the deposition of Fe atoms on tetracyanophenyl (Co-TCNPP) and tetrapyridyl-functionalized (Zn-TPPyP) porphyrins on Au(111) by means of scanning tunneling microscopy (STM). A comparative analysis of the influence of the cyano and pyridyl endgroups on the formation of different in-plane coordination motifs is performed. Each porphyrin derivative formed two structurally different Fe-coordinated MOCNs stabilized by three- and fourfold in-plane coordination nodes, respectively. Interestingly, the codeposited Fe atoms did not only bind to the functional endgroups but also reacted with the porphyrin core of the Zn-substituted porphyrin (Zn-TPyP), i.e., an atom exchange reaction took place in the porphyrin core where the codeposited Fe atoms replaced the Zn atoms. This was evidenced by the appearance of molecules with an enhanced (centered) STM contrast compared with the appearance of Zn-TPyP, which suggested the formation of a new molecular species, i.e., Fe-TPPyP. Furthermore, the porphyrin core of the Co-substituted porphyrin (Co-TCNPP) displayed an off-centered STM contrast after the deposition of Fe atoms, which was attributed to the binding of the Fe atoms on the top site of the Co-substituted porphyrin core. In summary, the deposition of metal atoms onto organic layers can steer the formation of structurally different MOCNs and may replace pre-existing metal atoms contained in the porphyrin core.

Development of dual-ligand titanium (IV) hydrophilic network sorbent for highly selective enrichment of phosphopeptides

A hydrophilic metal-organic network based on Ti4+ and dual natural ligand, tannic acid (TA) and phytic acid (PA), has been developed to enrich phosphopeptides from complex bio-samples prior to liquid chromatography-mass spectrometric analysis. Due to the strong chelation ability of TA and PA, abundant Ti4+ can be immobilized in the material, forming hydrophilic network by one-step coordination-driven self-assembly approach. The sorbent, TA-Ti-PA@Fe3O4, exhibited satisfactory selectivity for the phosphopeptides in the tryptic digest of β-casein, and can eliminate the interference components in 1000-fold excess of bovine serum albumin. The adsorption capacity of the sorbents for phosphopeptides was up to 35.2 mg g−1 and the adsorbing equilibrium can be reached in 5 min. The adsorbing mechanism has been investigated and the results indicated that the Ti4+ in forms of [Ti(f-TA)(H2O)4]2+, [Ti(f-PA)(H2O)4]2+ and Ti(f-PA)2(H2O)2 may play an important role in the adsorption process. The sorbent of the TA-Ti-PA@Fe3O4 has been applied to enrichment of the phosphopeptides in tryptic digest of rat liver lysate, and 3408 phosphopeptides have been identified, while the numbers of the identified phosphopeptides were 2730 and 1217 when the sample was enriched by the commercial TiO2 and Fe3+-IMAC kit, respectively. This work provides a strategy to enrich phosphopeptides from complex samples and shows great potential application in phosphoproteome research.

Steering Metal-Organic Network Structures through Conformations and Configurations on Surfaces.

Molecular adsorption conformations and arrangement configurations on surfaces are important structural aspects of surface stereochemistry, but their roles in steering the structures of metal-organic networks (MONs) remain vague and unexplored. In this study, we constructed MONs by the coordination self-assembly of isocyanides on Cu(111) and Ag(111) surfaces and demonstrated that the MON structures can be steered by surface stereochemistry, including the adsorption conformations of the isocyanide molecules and the arrangement configurations of the coordination nodes and subunits. The coordination self-assembly of 1,4-phenylene diisocyanobenzene afforded a honeycomb MON consisting of 3-fold (isocyano)3-Cu motifs on a Cu(111) surface. In contrast, geometrically different chevron-shaped 1,3-phenylene diisocyanobenzene (m-DICB) failed to generate a MON, which is ascribable to its standing conformation on the Cu(111) surface. However, m-DICB was adsorbed in a flat conformation on a Ag(111) surface, which has a larger lattice constant than a Cu(111) surface, and smoothly underwent coordination self-assembly to form a MON consisting of (isocyano)3-Ag motifs. Interestingly, only C3-Ag nodes with heterotactic configurations could grow into larger subunits; those subunits with heterotactic configurations further grew into Sierpiński triangle fractals (up to fourth order), while subunits with homotactic configurations afforded a triangular MON.

Fluorine Doped MOFs Based on Nickel and Manganese As Anode for Applications in Lithium-Ion Batteries

Lithium-ion batteries are energy storage devices that have become a fundamental part of our daily lives due to their use in electronic devices. Many materials are currently being researched due to the new requirements that are needed for this application. Metal organic networks (MOFs) are a type of material with unique properties such as high surface area, high porosity, good crystallinity, and functionality, which are formed by joining inorganic and organic units by coordination bonds, where the inorganic units are usually metal oxides that are active sites for redox processes. Transition metals (Fe, Co, Ni, Cr, etc.) are known to be precursors in the synthesis of MOFs with electrochemical activity, the presence of these unsaturated metals in the structure of MOFs as Lewis acids improves the electrochemical activity in catalytic processes. According to the characteristics and properties of MOFs, an efficient way to increase the specific charging capacity of batteries is the introduction of other redox active sites from another metal, as well as the choice of the appropriate ligand. This research proposes the solvothermal synthesis of MOFs based on nickel and manganese, with terephthalic acid in DMF solvent, as new anodic materials. The DRX analysis show the presence of the monometallic MOFs phases in the bimetallic MOF and the FT-IR spectra show the coordination of Ni and Mn with the BDC ligand. In addition, significant increase in the electrochemical properties was developed with the addition of F-, which will cause the destruction of the coordination bond of the metals with their ligands, improving the lithiation/de-lithiation process. Due to the presence of active redox sites, the affinity of fluorine for lithium and the synergistic effect that metals present in bimetallic MOF, it is expected that this material will present improved electrochemical properties to be used as an anode in lithium-ion batteries; and by reducing the amount in the manganese ratio, the material will improve its conductivity properties.This research is supported by the world bank and Prociencia through agreement No. 045-2019 FONDECYT-BM.

Comparing Zinc Oxide- and Zinc Silicate-Related Metal-Organic Networks via Connection-Based Zagreb Indices

Metal-organic networks (MONs) are among the unique complex and porous chemical compounds. So, these chemical compounds consist of metal ions (vertices) and organic ligands (edges between vertices). These networks represent large pore volume, extreme surface area, morphology, excellent chemical stability, highly porous and crystalline materials, and octahedral clusters. MONs are mostly used in assessment of chemicals, gas and energy storage devices, sensing, separation and purification of different gases, heterogeneous catalysis, environmental hazard, toxicology, adsorption analysis, biomedical applications, and biocompatibility. Recently, drug delivery, cancer imaging, and biosensing have been investigated by biomedical applications of zinc-related MONs. The versatile applications of these MONs make them helpful tools in many fields of science in recent decade. In this paper, we discuss the two different zinc oxide and zinc silicate related MONs according to the number of increasing layers of metal and organic ligands together. We also compute the connection-based Zagreb indices such as first Zagreb connection index (ZCI), second ZCI, modified first ZCI, modified second ZCI, modified third ZCI, and modified fourth ZCI. Moreover, a comparison is also included between the zinc-related MONs by using numerical values of connection-based Zagreb indices. Finally, we conclude that zinc silicate-related MON is better than zinc oxide-related MON for all values of n.

Multi-functional epoxy composite coating incorporating mixed Cu(II) and Zr(IV) complexes of metformin and 2,2\-bipyridine as intensive network cross-linkers exhibiting anti-corrosion, self-healing and chemical-resistance performances for steel petroleum platforms

Metal-organic network cross-linking agents are commingled with epoxy for establishing multi-functional coating system with robust resistance properties for steel protection applications in harsh atmospheres. To support this concept, the present study relates to fabrication of new mixed ligand Cu(II) and Zr(IV) complexes of metformin (MF) and 2.2′bipyridine (bpy) as coating surface cross-linking modifiers to guard the steel surface of petroleum platforms from corrosion in severe environments. CHN analysis, molar conductance, magnetic susceptibility, FT-IR, UV–Visible, 1 H NMR and TGA/DTG analysis were performed for full characterizations of the two ligands and their mixed complexes. The elemental analysis data affirmed the chemical formula of the formed complexes. Molar conductance measurements proved that the complexes were electrolytic in nature with 1:2 (metal:ligand) molar ratio. The FT-IR analysis for MF, bpy and their complexes manifested that MF and bpy chelated with metal ions as bidentate ligands through two imines (-C = NH) groups in MF and through two nitrogen of pyridine rings in bpy. The TGA/DTG analysis demonstrated the thermal stability and decomposition of the complexes. The magnetic moment measurements offered paramagnetic properties for Cu(II), μ eff = 1.70 B.M. The structure geometry survey affirmed a distorted octahedral geometry of the formed Cu(II) and Zr(IV) complexes. Epoxy coating formulations loaded with the same concentration of MF, bpy, Cu(II), and Zr(IV) compounds were applied and evaluated. Salt spray corrosion trial demonstrated that PA-DGEBA/MC-Cu coating achieved advanced corrosion mitigation demeanor at blistering size of #8, few frequency and calculated rust grade at 10. SEM morphology and EDX analysis were performed to explicate the protective performance in which PA-DGEBA/MC-Cu coated layer displayed the least Fe peak count at 2.5 without appearance of rusting. AFM microstructure of surface-modified Cu(II) epoxy coating offered the most smooth surface (Ra = 1.78 nm, Rq = 2.99 nm), with a harder matrix and perfect nonporous coating surface. Acid spot test checked the chemical resistance of these coatings and elucidated that DGEBA/MC-Cu coating achieved the highest acid resistances at Level 0 by H 2 SO 4 (96%), HNO 3 (70%) and HCl (37%) against full deterioration of blank neat epoxy at Level 3.

Fast deposition of Fe3+ chelated tannic acid network via salt induction over graphene oxide based SBS modified asphalt

Herein, fast and uniform deposition of tannic acid iron ion self-assembled metal–organic network (Fe3+-TA) was established using salt induction strategy over graphene oxide (GO) based styrene butadiene styrene (SBS) support (Fe3+-TA-GO/SBS) to prepare modified asphalt. Mechanical properties of the SBS modified asphalt (SBS-MA), GO/SBS-MA, and Fe3 + -TA-GO/SBS-MA were systematically studied via dynamic shear rheometer, multiple stress creep recovery test, and thermogravimetric analysis. The mechanism of Fe3+-TA-GO in SBS-MA was elucidated by Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. Results showed that the penetration of 0.10 % Fe3+-TA-GO/SBS-MA is 38.3 % lower than that of SBS-MA, which indicates excellent viscoelastic properties, rutting resistance, and thermal stability 0.10 % Fe3+-TA-GO/SBS-MA modified asphalt. This green biomimetic modification method effectively solves the agglomeration problem of GO in asphalt and promotes the formation of a well-developed SBS network structure in Fe3+-TA-GO/SBS-MA, which could be considered as a promising approach for the preparation of modified asphalt with enhanced properties for practical applications.

Computing Novel Multiplicative Zagreb Connection Indices of Metal Organic Networks

Metal organic networks (MONs) are defined as one, two and three dimensional unique complex structures of porous material and subclass of polymer’s coordination. These networks also show extreme surface area, morphology, excellent chemical stability, large pore volume, highly crystalline materials. The major advantages of MONs are tailorability, structural diversity, versatile applications, highly controllable nano-structures and functionality. So, the multi-functional applications of these MONs are made them more helpful tools in many fields of science in recent decade. In this paper, we light on the two different MONs with respect to the number of increasing layers of metal and organic ligands together. We define the novel multiplicative Zagreb connection indices (ZCIs) such that multiplicative fourth ZCI and multiplicative fifth ZCI. We also compute the main results for multiplicative Zagreb connection indices of two different MONs (zinc oxide and zinc silicate).

Tuning the Magnetic Anisotropy of Lanthanides on a Metal Substrate by Metal–Organic Coordination (Small 35/2021)

Magnetic Anisotropy The magnetism of lanthanide-directed nanoarchitectures on surfaces can be drastically affected by small structural changes. In article number 2102753, Sofia Parreiras, Paolo Perna, David Écija, and co-workers report the effect of the coordination environment in the reorientation of the magnetic easy axis of dysprosium-directed metal-organic networks on Cu(111). The authors show that the magnetic anisotropy of lanthanide elements on surfaces can be tailored by specific coordinative metal–organic protocols.

Toward a Greener World-Cyclodextrin Derivatization by Mechanochemistry.

Cyclodextrin (CD) derivatives are a challenge, mainly due to solubility problems. In many cases, the synthesis of CD derivatives requires high-boiling solvents, whereas the product isolation from the aqueous methods often requires energy-intensive processes. Complex formation faces similar challenges in that it involves interacting materials with conflicting properties. However, many authors also refer to the formation of non-covalent bonds, such as the formation of inclusion complexes or metal–organic networks, as reactions or synthesis, which makes it difficult to classify the technical papers. In many cases, the solubility of both the starting material and the product in the same solvent differs significantly. The sweetest point of mechanochemistry is the reduced demand or complete elimination of solvents from the synthesis. The lack of solvents can make syntheses more economical and greener. The limited molecular movements in solid-state allow the preparation of CD derivatives, which are difficult to produce under solvent reaction conditions. A mechanochemical reaction generally has a higher reagent utilization rate. When the reaction yields a good guest co-product, solvent-free conditions can be slower than in solution conditions. Regioselective syntheses of per-6-amino and alkylthio-CD derivatives or insoluble cyclodextrin polymers and nanosponges are good examples of what a greener technology can offer through solvent-free reaction conditions. In the case of thiolated CD derivatives, the absence of solvents results in significant suppression of the thiol group oxidation, too. The insoluble polymer synthesis is also more efficient when using the same molar ratio of the reagents as the solution reaction. Solid reactants not only reduce the chance of hydrolysis of multifunctional reactants or side reactions, but the spatial proximity of macrocycles also reduces the length of the spacing formed by the crosslinker. The structure of insoluble polymers of the mechanochemical reactions generally is more compact, with fewer and shorter hydrophilic arms than the products of the solution reactions.

Role of the Structure and Reactivity of Cu and Ag Surfaces in the Formation of a 2D Metal–Hexahydroxytriphenylene Network

We have investigated the role played by the atomic structure and reactivity of the supporting Ag(111) and Cu(111) surfaces on the formation of 2D metal–organic networks (2D-MONs) involving metal adatom clusters spawned by these two surfaces. While the hexahydroxytriphenylene (HHTP) molecule forms complexes with Ag3 and Cu3 adatom clusters on, respectively, the Ag(111) and Cu(111) surfaces, an extended order is only observed in the 2D-MON on Ag(111). By combining scanning tunneling microscopy measurements, density functional theory calculations, and microscopy image simulations, we show that the formation of Ag–HHTP metal–organic complexes is structurally compatible with a periodic arrangement of HHTP on the Ag(111) surface. In contrast, on Cu(111), tightly bonded and localized Cu–HHTP motifs are stabilized by the interaction of Cu adclusters with HHTP. However, they cannot match the surface structure of Cu(111) to form an extended 2D-MON. We observed that the formation of large 2D-MON domains on a metallic surface is only possible when the periodicity of the adsorbed surface assembly is weakly perturbed by the addition of metal adclusters that reinforced the bonding.

Tuning the Magnetic Anisotropy of Lanthanides on a Metal Substrate by Metal-Organic Coordination.

Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy-carboxylate metal-organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X-ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface-supported metal-organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in-plane easy magnetization axis despite the out-of-plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal-organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces.

Structural and Thermal Investigations of Co(II) and Ni(II) Coordination Polymers Based on biphenyl-4,4'-dioxydiacetate Linker.

Two coordination polymers, [Co(µ4-L)(H2O)2]n (1) and [Ni(µ-L)(H2O)4]n (2), were solvothermally assembled from the corresponding metal(II) chlorides and biphenyl-4,4-dioxydiacetic acid (H2L) as a flexible dicarboxylate linker. The cobalt(II) compound 1 featured a layer-pillared 3D metal-organic network with a cds topology, while the nickel(II) derivative 2 represented a linear chain 1D coordination polymer with a 2C1 topology. The µ4− and µ-L2− linkers exhibited different denticity and coordination modes in the synthesized compounds, thus contributing to their structural diversity. The dimensionality of 1 and 2 had an influence on their thermal stability and decomposition processes, which were investigated in detail by TG-DSC and TG-FTIR methods. Thermal decomposition products of coordination polymers were also analyzed by PXRD, confirming the formation of Co3O4/CoO and NiO as final materials. The obtained compounds broaden a family of coordination polymers assembled from flexible dicarboxylate linkers.

Tailoring the redox capabilities of organic ligands for metal-ligand coordination with vanadium single-sites

The creation of single-site metal centers (SSMCs) through the formation of metal-organic coordination networks is an area of interest due to the proven ability of SSMCs to improve selectivity for heterogeneous catalysts. In order to better understand the reactivity potential for the SSMCs it is necessary to study the ligand-metal interaction in the metal-organic coordination networks. In the work reported here, we demonstrate the ability to tune the oxidation state of vanadium from II to IV through the tailoring of redox-active ligands. Using the N-heterocyclic ligands of bipyrimidine (BP), bispyrimidinyltetrazine (BMTZ), and biimidazole (BIM) complexed with metallic V, we have shown that the oxidation state of the V metal centers can be tuned to V(II) for BP, V(III) for BMTZ, and V(IV) for BIM. These redox-active ligands provide similar coordination environments when complexed into one dimensional chains but result in different oxidation states for the single-site metal center.

Syntheses, structures and adsorption properties of 2D rare earth metal organic networks based on Keggin type polyoxometalate as bidentate ligand

Two Keggin-type polyoxometalates (POMs)-based rare-earth metal–organic networks, namely, [CeIV (BPDO)3(H2O)3][SiW12O40] (1, CCDC 1981416) and [PrIII(BPDO)3(H2O)3]H[SiW12O40] (2, CCDC 1981407) have been synthesized under mild hydrothermalcondition (160 °C for 72 h) in the presence of 4,4′-bipyridine-N-dioxide (BPDO) ligand and Keggin-anions [SiW12O40]4−. Both compounds exhibit similar 2D layer structures constructing by typically saturated Keggin-anions [SiW12O40]4− as bidentate bridging ligand, in spite of the large steric hindrance. Our work definitely provides a new possibility to access intricate topologies, especially in highly connected networks. In addition, the adsorption properties of the compounds have been primarily investigated. From the point view of equilibrium time (<1 h) and removal efficiency (close to 100%), the incorporation of Keggin-anions plays an important role in the fast capture of cationic dye MB+.

A hydrogel-like form-stable phase change material with high loading efficiency supported by a three dimensional metal–organic network

• We prepared a hydrogel-like form-stable phase change material (FSPCM). • This FSPCM is supported by a three dimensional metal–organic network. • This FSPCM has a loading efficiency of 98.0 wt% for polyethylene glycol. We prepared a hydrogel-like polyethylene glycol (PEG)-based form-stable phase change material (FSPCM) supported by a three dimensional (3D) metal–organic network through a very simple method with low cost. The 3D network with ultrahigh molecular weight and crosslinking density has strong hydrogen bonding interaction with PEG molecules, and keeps the PEG matrix shape-stabilized even at 80 °C. Like hydrogels that can retain substantial water, this hydrogel-like FSPCM has a loading efficiency for PEG of 98.0 wt%, which is the highest value of PEG-based FSPCMs until now to the best of our knowledge. The latent heat values of the FSPCM are 158.4 and 165.3 J·g −1 in the melting and solidification process respectively, showing remarkable performance for thermal energy storage. Additionally, the hydrogel-like FSPCM has excellent thermal reliability due to the stable structure and property of the 3D metal–organic network.