Linker of two-dimensional polymer, monomolecular layer assembly method thereof, and two-dimensional molecular preassembly

Abstract

The invention belongs to the field of organic synthesis, and particularly relates to a connector of a two-dimensional polymer, a monomolecular layer assembling method of the connector and a two-dimensional molecular preassembly. The linker is a molecule comprising a linker molecular core and at least one linking group; the linking group comprises at least one first type of functional group combined with the two-dimensional polymer, and the linker molecule at least comprises two first type of functional groups; the bonding at least comprises chemical bonding; the connectors and the two-dimensional polymers are combined in any number to form a layered polymer, and the thickness of the layered polymer is two times smaller than that of a single two-dimensional polymer. The connector disclosed by the invention can be universally suitable for assembling and combining almost all two-dimensional polymer molecules to construct a required two-dimensional assembly and / or a pre-assembly, and can be used for simultaneously assembling different types of two-dimensional polymer molecules to construct a novel composite two-dimensional molecular assembly to realize functionalization; and the method has wide universality, effectiveness and high efficiency.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, and particularly relates to the linkers of two-dimensional polymers and their monolayer assembly methods, as well as two-dimensional molecular pre-assemblies. Background Technology

[0002] Since the successful exfoliation of graphene, two-dimensional (2D) materials, with their unique atomic-level thickness, huge specific surface area, and the novel physicochemical properties derived from them, have completely changed the research paradigm of materials science, physics, and chemistry. However, the intrinsic properties of inorganic two-dimensional materials such as graphene and transition metal sulfides (TMDs) are relatively fixed, making it difficult to achieve precise functional regulation through chemical methods.

[0003] To overcome this limitation, researchers have turned their attention to the field of organic chemistry, and two-dimensional polymers (2DPolymers, 2DPs) have gained significant attention in the materials science field. As a novel class of polymeric materials that extend infinitely within a two-dimensional plane through covalent bonds, 2DPs exhibit enormous application potential in electronics, energy storage, separation membranes, and catalysis due to their unique structural regularity, designable chemical functionality, and excellent physicochemical properties.

[0004] Traditionally, two-dimensional polymers (also known as two-dimensional macromolecules) are usually defined as sheet-like macromolecules formed by connecting structural units (monomer small molecules) in a plane (two dimensions) through strong covalent bonds. Or, more broadly, they are polymer molecules formed by connecting several structural units with a thickness less than twice the thickness of the structural units. They can also be regarded as two-dimensional polymers in a general sense because their polymerization process does not spill over into a third dimension and has obvious dimensionality.

[0005] Currently, the term "two-dimensional polymer" is often used to refer to inorganic carbon materials such as graphene and graphene oxide, or organic crystals such as two-dimensional covalent organic frameworks (2D COFs). It's important to note that, as stated in the paper "Two-dimensional polymers: concepts and perspectives," a more rigorous academic definition would not classify these materials as standard two-dimensional polymers. This is because the definition of a two-dimensional polymer has two key elements: the thickness of the polymer is close to that of the monomer (precisely defined in this paper as less than twice the thickness of the monomer); and the aggregates of these two-dimensional polymers can be completely dispersed into single molecules through dissolution, mechanical action, or other means. According to the definition in the aforementioned paper, insoluble and infusible 2D COF powders composed of polycrystalline materials are merely three-dimensional crystalline materials with two-dimensional characteristics, and do not belong to the category of true two-dimensional polymers. This is because the monomer connections within the COF structure are dynamic covalent bonds (weak, reversible covalent bonds). These weak and reversible covalent bonds cannot remain stable under acidic or alkaline solvents and strong mechanical stress. Therefore, these materials cannot be obtained as high-proportion, monodisperse 2D sheet-like polymers through direct dissolution in acidic or alkaline solvents (the product is first ionized by acid or base before dissolution) or ultrasonic exfoliation (strong mechanical physical exfoliation). In general, the construction of the COF framework structure highly depends on the structural error correction capability brought about by dynamic covalent bonds. However, it is precisely these weak covalent bonds that inevitably make COFs have low thermodynamic stability. More seriously, the crystallization process required for synthesis has harsh requirements on reaction conditions (high temperature, high pressure, long-term solvothermal reaction), making the stability and scalability of this type of material synthesis very poor. Due to the lack of high reversibility, crystallinity cannot be constructed. These fatal weaknesses of COF, as intrinsic properties of the material, cannot be solved at the underlying principle level. Therefore, although this type of material has existed for thirty years, there are still no reports of large-scale applications.

[0006] Unlike thin films assembled from traditional inorganic two-dimensional materials (such as graphene, hexagonal boron nitride, and molybdenum disulfide) that are stacked through weak interactions like van der Waals forces and exhibit only a two-dimensional morphology on a macroscopic scale, 2DPs are all-organic structures with a richer variety of chemical structures and more diverse intermolecular interaction modes. This diversity of intramolecular structures and intermolecular interactions endows them with a series of unparalleled advantages, such as structural designability, functional diversity, and excellent mechanical, mass transfer, and barrier properties. Based on these potential advantages, 2DPs are considered ideal candidate materials for next-generation high-performance separation membranes (such as gas separation and water purification), flexible electronic device energy storage and conversion (such as batteries and supercapacitors), and heterogeneous catalysis.

[0007] However, the core bottleneck lies in how to prepare high-quality monolayer two-dimensional polymer molecular films. Only when the material exists in a monolayer or controllable few-layer form with large area, low defects, and high stability can its two-dimensional properties be maximized.

[0008] Despite the rapid advancements in the synthetic chemistry of 2DPs over the past decade, the controllable preparation of high-quality monolayer membranes remains a significant challenge. In practical synthesis, polymerization reactions are often difficult to confine perfectly within a two-dimensional plane, easily leading to the formation of amorphous three-dimensional byproducts. Simultaneously, issues such as polycrystalline nucleation and heterogeneous monomer arrangement inevitably result in numerous defects in the film, including grain boundaries, vacancies, and wrinkles. These defects severely impair the film's mechanical strength, charge transport efficiency, and selective permeation properties, causing it to fall far short of theoretical expectations.

[0009] To achieve ordered connections in a two-dimensional plane, researchers have developed a variety of ingenious synthetic strategies. The core idea behind these strategies is to utilize physical or chemical "spatial confinement" to guide the polymerization reaction. Currently, the mainstream research directions can be summarized as follows: interfacial polymerization, CVD (chemical vapor deposition), and solution methods (wet chemical methods). Among these, interfacial polymerization is currently the most important method for synthesizing two-dimensional polymer films, especially monolayer or few-layer films, and is one of the most commonly used and successful methods. Its basic principle is to use the two-dimensional interface formed by two immiscible phases (such as gas-liquid or liquid-liquid) as a reaction platform. The reactants are dissolved in both phases, or one monomer is located at the interface while the other diffuses from the bulk phase to the interface. The polymerization reaction is strictly confined within this two-dimensional space. CVD and solution methods can also achieve the preparation of two-dimensional polymer monolayer or few-layer films.

[0010] However, all of the above-mentioned main methods have many drawbacks. As documented in literature such as "2D Conjugated Polymer ThinFilms for Organic Electronics: Opportunities and Challenges" and "2D Polymer Nanosheets for Membrane Separation", interfacial polymerization methods generally suffer from difficulties in ensuring film quality and uniformity. This is mainly due to the difficulty of the transfer process and the fact that the small size of the monomers makes it very easy to introduce wrinkles, cracks, and contaminants during transfer. Furthermore, the rate of interfacial polymerization is controlled by multiple factors such as monomer diffusion, interfacial adsorption, and catalyst activity, resulting in a very complex reaction kinetic model, low overall efficiency, and high cost, leading to a low cost-performance ratio. CVD methods, as documented in literature such as "Large-Screen Synthesis of Two-Dimensional Polymers and Their Membrane Applications," suffer from stringent reaction conditions and equipment requirements. Simultaneously ensuring extremely high thermal stability and suitable volatility of the monomers leads to high material and equipment costs, limited applicability, and difficulty in synergistically controlling nucleation density, domain growth rate, and domain orientation to reduce grain boundary and point defect formation. Similarly, the same paper also notes that while solution methods are low-cost, scalable, and suitable for industrial production, the products exhibit poor two-dimensionality, with most remaining three-dimensional stacked microcrystalline aggregates. Obtaining single-layer or few-layer nanosheets necessitates a post-processing exfoliation step. However, exfoliation processes are typically inefficient, yield extremely low outputs, and are violent, severely damaging the structural integrity of the nanosheets and introducing numerous defects.

[0011] In summary, neither the preparation of COF single-crystal powders with two-dimensional layered characteristics via reversible chemical methods, nor the fabrication of large-area monolayer or oligolayer two-dimensional polymer films via two-dimensional template methods (interfacial polymerization and CVD, etc.) can simultaneously meet the fundamental requirements for materials in large-scale industrial applications: chemical stability, mass production capability, low cost, and convenient exfoliation / transfer. Therefore, current methods for effectively preparing two-dimensional polymer monolayer products, i.e., constructing two-dimensional molecular assemblies, still require innovation and development in underlying technologies. Summary of the Invention

[0012] To address the challenges of preparing generalized two-dimensional monolayer polymer films with a thickness less than twice that of the precursor and / or monomer, which are often limited by high preparation costs, stringent preparation conditions, and the fact that most precursors are small monomer molecules, making it difficult to effectively control structure and performance and lacking the universality required for industrialization, this invention provides a linker for two-dimensional polymers and its monolayer assembly method, as well as two-dimensional molecular pre-assemblies.

[0013] The main objective of this invention is: I. This invention provides a universal linker molecule and a method for selecting the linker molecule. The linker molecule can be substantially used for the recombination of all two-dimensional polymer molecules to form a monolayer film, and is not limited to the construction of a monolayer film with monomer molecules. Second, this invention provides a more specific assembly method adapted to linker molecules. By selecting linker molecules and assembly methods, it can be applied to the effective re-polymerization of almost all existing standard two-dimensional polymer molecules and some quasi-two-dimensional polymer molecules with near-two-dimensional structures within the quasi-planar range to construct monolayer films. Third, the linker molecules of this invention can very effectively maintain the two-dimensional planar structure characteristics of the two-dimensional polymer and form very effective and stable chemical bond connections, ensuring that the formed two-dimensional molecular assembly has extremely high structural stability.

[0014] To achieve the above objectives, the present invention adopts the following technical solution.

[0015] Two-dimensional polymer linkers The linker is a molecule comprising a linker molecular core and at least one linker group; The general molecular structure of the linker is shown in Formula 1 below: Formula 1: ; In Equation 1: P is the core of the linker molecule and it is an organic group with a valence state ≥1; R is the linker group; x is the number of types of linker groups and x≥1; y is the total number of linker groups and y≥1. The linking group includes at least one type-first functional group that can bind to a two-dimensional polymer; The linker molecule contains at least two type I functional groups; The combination includes physical bonding and / or chemical bonding, and at least one linking group contains at least one first type of functional group that can be chemically bonded to a two-dimensional polymer; The connectors are combined with any number of two-dimensional polymers to form a layered polymer, and the thickness of the layered polymer is less than twice the thickness of a single two-dimensional polymer.

[0016] As a preferred option The chemical bonds are interactions with bond energies ≥ 60 kJ / mol.

[0017] As a preferred option The physical bonding methods include hydrogen bonding and / or van der Waals force bonding and / or π-π stacking bonding and / or electrostatic bonding and / or host-guest inclusion bonding; The chemical bonding is in the form of covalent bonding and / or coordination bonding and / or ionic bonding, and includes at least covalent bonding.

[0018] As a preferred option The general structural formula of the linking group is shown in Formula 2 and / or Formula 3 below: Formula 2: ; Formula 3: ; In Equations 2 and 3: R' is the linker arm, R1 is the first type of functional group, and a is the number of first type of functional groups in a single linker group, and a≥1.

[0019] As a preferred option The first type of functional group is a covalently bonded functional group and / or a coordinate bonded functional group and / or a physically bonded functional group.

[0020] As a preferred option The covalently bonded functional groups include electrophilic functional groups and / or nucleophilic functional groups and / or click chemistry functional groups and / or cyclization functional groups and / or photoinitiation functional groups and / or thermal initiation functional groups; The coordination-bonded functional groups include metal central functional groups and / or complementary ligand functional groups; The physically bonded functional groups include π-system functional groups and / or charged functional groups and / or hydrophobic functional groups and / or hydrophilic functional groups and / or host-guest recognition functional groups and / or hydrogen bond donor functional groups and / or hydrogen bond acceptor functional groups.

[0021] As a preferred option The electrophilic functional groups include succinimide ester group and / or isocyanate group and / or epoxy group and / or aldehyde group and / or acyl chloride group and / or maleimide group and / or vinyl sulfone group and / or haloalkyl group; The nucleophilic functional groups include amino and / or thiol and / or hydroxyl and / or hydrazide and / or hydrazide and / or carboxyl group and / or sodium alkoxide and / or thiolate group; The functional groups of the click chemistry reaction include alkynyl and / or azide and / or tetraazinyl and / or norbornenyl; The cyclization functional groups include dienes and / or hydrogen dienes; The metal central functional group includes transition metal ions and / or rare earth metal ions and / or main group metal ions and / or their complexes. The complementary ligand functional groups include carboxyl groups and / or acetylaceton groups and / or benzoylmethane derivatives and / or phenoxy groups and / or alcoholoxy groups and / or amino groups and / or imino groups and / or aromatic nitrogen heterocycles and / or thiols and / or thiophenol groups and / or triphenylphosphine and / or diphenylphosphine, as well as pyridyl groups and / or bipyridyl groups and / or o-phenanthroline groups and / or carboxyl groups and / or phosphate groups and / or aminocarboxylic acid ligands and / or histidine tags, etc. The π-system functional groups include carbamoyl groups and / or heterocyclic aromatic groups and / or their derivatives, such as pyrene and / or perylene imide and / or porphyrin and / or phthalocyanine and / or tetraphenyl and / or crown ether aromatic derivatives, etc. The hydrophobic functional groups include long-chain alkyl and / or aryl and / or perfluoroalkyl and / or polysiloxane and / or ester groups. The hydrophilic functional groups include ionic groups and / or polyether chains and / or polyol groups and / or betaine-type zwitterionic groups; The charged functional groups include quaternary ammonium salt cations and / or phosphonium salt cations and / or sulfonate anions and / or carboxylate anions and / or phosphate anions; The host-guest recognition functional groups include cyclodextrin derivatives and / or calixarene derivatives and / or adamantyl and / or ferrocene and / or specific organic ammonium salts; The hydrogen bond donor functional groups include amino and / or amide and / or urea and / or carboxylic acid and / or phenolic hydroxyl groups; The hydrogen bond acceptor functional groups include carbonyl and / or ether and / or ester and / or pyridine nitrogen and / or sulfonyl groups.

[0022] As a preferred option The molecular core is a molecular core containing a rigid or semi-rigid linear structure and / or a symmetrical planar aromatic ring and / or a symmetrical conjugated structure and / or a rigid structure with a three-dimensional configuration and / or a flexible segment structure.

[0023] As a preferred option The molecular core is a molecular core containing an aromatic alkyne structure and / or an aromatic ene structure and / or a heterocyclic straight-chain structure and / or a conjugated rod structure and / or a rigid non-conjugated rod structure and / or a triazine symmetric structure and / or a six-fold symmetric structure and / or a four-fold square symmetric structure and / or a triangular symmetric structure and / or a rhombic symmetric structure and / or a spirocyclic central structure and / or a tetrahedral central structure and / or a cage-like molecular structure and / or a basket-like molecular structure and / or a flexible alkane chain structure and / or a polyethylene glycol chain structure and / or a siloxane chain structure.

[0024] As a preferred option The molecular core comprises 1,4-diethynylbenzene and / or 4,4'-diaminodiphenylacetylene and / or 1,3,5-tris(4-aminophenyl)benzene and / or tetra(4-aminophenyl)porphyrin and / or 9,9'-spirodifluorene-2,7-diboronic acid and / or tetra(4-carboxyphenyl)silane and / or 1,4-phenyldiboronic acid and / or naphthalene-1,4-diboronic acid and / or 2,5-dimethoxyterephthalohydrazide and / or 2,5-bis(2-methoxyethoxy)terephthalohydrazide Formic acid hydrazide and / or 2,3,6,7,10,11-hexahydroxytriphenyl and / or 4,4'-(1,3-adamantanediyl)diphenyl and / or 9,10-anthraquinone and / or 2,7-dihydroxynaphthalene and / or 2,6-naphthoquinone and / or 1,4-dihydroxynaphthalene and / or [1,1':4',1'':4'',1'''-tetraphenyl]-3,3''',5,5'''-tetracarboxaldehyde and / or spirocyclic diol and / or spirocyclic diamine and / or 3,6-dibromo- 9,9'-spirofluorene and / or 5'-(3,5-dicarboxyphenyl)-[1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxaldehyde and / or 5',5''-bis(4-formylphenyl)-[1,1':3',1'':3'',1'''-tetraphenyl]-4,4'''-dicarboxaldehyde and / or 5-(4-formyl-[1,1-biphenyl]-4-yl)-[1,1:4,1:3,1:4, [1-Quinophenyl]-4,4-dicarboxaldehyde and / or 1,3,5-tris(4-carboxyphenyl)benzene and / or 5',5''-bis(4-formylphenyl)-2',2'',4',4'',6',6''-hexamethyl-[1,1':3',1'':3'',1'''-tetraphenyl]-4,4'''-dicarboxaldehyde and / or 4,4'-(1,2-diphenylvinyl-1,2-diyl)biphenol and / or hexa(4-aminobiphenyl)benzene.

[0025] As a preferred option The molecular core contains a symmetrical planar aromatic ring structure and / or a rigid structure with a three-dimensional configuration.

[0026] As a preferred option The molecular core contains a six-fold symmetry structure and / or a four-fold square symmetry structure and / or a triangular symmetry structure and / or a rhomboid symmetry structure and / or a spiral ring center structure.

[0027] Among these, 1,4-phenylenediboronic acid and / or naphthalene-1,4-diboronic acid and / or 2,5-dimethoxyterephthalohydrazide and / or 2,5-bis(2-methoxyethoxy)terephthalohydrazide and / or 2,3,6,7,10,11-hexahydroxytriphenyl and / or 4,4'-(1,3-adamantanediyl)diphenyl and / or 9,10-anthradinol and / or 2,7-dihydroxynaphthalene and / or 2,6 -Naphthodiol and / or 1,4-dihydroxynaphthyl and / or [1,1':4',1'':4'',1'''-tetraphenyl]-3,3''',5,5'''-tetracarboxaldehyde and / or spirocyclodiol and / or spirocyclodiamine and / or 3,6-dibromo-9,9'-spirofluorene and / or 5'-(3,5-dicarboxyphenyl)-[1,1':3',1''-terphenyl]-3,3'',5,5 ''-Tetracarboxaldehyde and / or 5',5''-bis(4-formylphenyl)-[1,1':3',1'':3'',1'''-tetraphenyl]-4,4'''-dicarboxaldehyde and / or 5-(4-formyl-[1,1-biphenyl]-4-yl)-[1,1:4,1:3,1:4,1-quinoline]-4,4-dicarboxaldehyde and / or 1,3,5-tris(4-carboxyphenyl)benzene and / Or 5',5''-bis(4-formylphenyl)-2',2'',4',4'',6',6''-hexamethyl-[1,1':3',1'':3'',1'''-tetraphenyl]-4,4'''-dicarboxaldehyde and / or 4,4'-(1,2-diphenylvinyl-1,2-diyl)biphenol and / or hexa(4-aminobiphenyl)benzene, etc., have a molecular core with better theoretical performance.

[0028] Monolayer assembly methods for two-dimensional polymers The method includes: Two-dimensional polymer molecules and the linkers as described in any one of claims 1 to 12 are assembled and combined once or multiple times to form a two-dimensional molecular assembly in a single-layer space through the assembly and combination of the linkers and the two-dimensional polymer. The thickness of the two-dimensional molecular assembly is less than twice the thickness of the two-dimensional polymer molecule; In the two-dimensional molecular assembly, there is at least one chemical bond between the linker and any of the two-dimensional polymer molecules it is bonded to.

[0029] As a preferred option The assembly and bonding methods include solvent-induced assembly and / or photochemical assembly and / or thermochemical assembly and / or electrochemical assembly and / or interface assembly and / or template-assisted assembly and / or self-assembly and / or mechanochemical assembly and / or biomolecular-assisted assembly and / or chemical vapor deposition assembly and / or epitaxial growth assembly.

[0030] As a preferred option The assembly methods include solvent evaporation-induced assembly and / or solvent exchange-induced assembly and / or solvent polarity modulation assembly and / or antisolvent addition-induced assembly and / or ultraviolet light-induced assembly and / or visible light-induced assembly and / or infrared light-induced assembly and / or photoisomerization-induced assembly and / or photopolymerization-induced assembly and / or heat treatment assembly and / or thermal gradient-induced assembly and / or thermally induced phase change assembly and / or thermal polymerization-induced assembly and / or DC electrochemical assembly and / or pulsed electrochemical assembly and / or AC electrochemical assembly and / or electrochemical deposition assembly and / or electrochemical polymerization assembly and / or Langmuir-Blodgett assembly and / or liquid-liquid interface assembly and / or gas-liquid interface assembly. Assembly and / or solid-liquid interface assembly and / or hard template assembly and / or soft template assembly and / or biological template assembly and / or patterned template assembly and / or molecular self-assembly and / or supramolecular self-assembly and / or block copolymer self-assembly and / or electrostatic self-assembly and / or ultrasound-assisted assembly and / or shear-induced assembly and / or ball milling-induced assembly and / or pressure-induced assembly and / or DNA origami-guided assembly and / or enzyme-catalyzed assembly and / or protein-assisted assembly and / or carbohydrate-mediated assembly and / or low-pressure CVD assembly and / or plasma-enhanced CVD assembly and / or organometallic CVD assembly and / or atomic layer deposition-assisted assembly and / or van der Waals epitaxy assembly and / or coherent epitaxy assembly and / or step-guided assembly.

[0031] As a preferred option The assembly and bonding methods include photochemical assembly and / or thermochemical assembly and / or interface assembly and / or template-assisted assembly.

[0032] As a preferred option The assembly and bonding methods include photochemical assembly and / or thermochemical assembly.

[0033] As a preferred option The assembly and bonding methods include ultraviolet light-induced assembly and / or visible light-induced assembly and / or infrared light-induced assembly and / or photo-isomerization-induced assembly and / or photopolymerization-induced assembly and / or thermal treatment assembly and / or thermal gradient-induced assembly and / or thermally induced phase change-induced assembly and / or thermal polymerization-induced assembly and / or Langmuir-Blodgett assembly and / or hard template assembly and / or soft template assembly and / or biological template assembly and / or patterned template assembly.

[0034] As a preferred option The assembly and bonding methods include ultraviolet light-induced assembly and / or visible light-induced assembly and / or infrared light-induced assembly and / or photo-isomerization-induced assembly and / or photopolymerization-induced assembly and / or thermal treatment assembly and / or thermal gradient-induced assembly and / or thermally induced phase change-induced assembly and / or thermal polymerization-induced assembly and / or Langmuir-Blodgett assembly.

[0035] As a preferred option In the two-dimensional molecular assembly, a single two-dimensional polymer molecule is connected to one or more linkers, and a single linker is connected to one or more two-dimensional polymer molecules.

[0036] As a preferred option The two-dimensional polymer molecule is a polymer molecule whose thickness is less than twice the thickness of its monomer molecule before polymerization.

[0037] As a preferred option The two-dimensional polymer contains a second type of functional group that binds to the linker; The second type of functional group is located at the ends and / or edges of the two-dimensional polymer molecule.

[0038] As a preferred option The second type of functional group is a covalently bonded functional group and / or a coordinate bonded functional group and / or a physically bonded functional group.

[0039] As a preferred option The covalently bonded functional groups include electrophilic functional groups and / or nucleophilic functional groups and / or click chemistry functional groups and / or photoinitiating functional groups and / or thermal initiating functional groups; The coordination-bonded functional groups include metal central functional groups and / or complementary ligand functional groups; The physically bonded functional groups include π-system functional groups and / or charged functional groups and / or hydrophobic functional groups and / or hydrophilic functional groups and / or host-guest recognition functional groups and / or hydrogen bond donor functional groups and / or hydrogen bond acceptor functional groups.

[0040] As a preferred option The electrophilic functional groups include succinimide ester group and / or isocyanate group and / or epoxy group and / or aldehyde group and / or acyl chloride group and / or maleimide group and / or vinyl sulfone group and / or haloalkyl group; The nucleophilic functional groups include amino and / or thiol and / or hydroxyl and / or hydrazide and / or hydrazide and / or carboxyl group and / or sodium alkoxide and / or thiolate group; The functional groups of the click chemistry reaction include alkynyl and / or azide and / or tetraazinyl and / or norbornenyl; The metal central functional group includes transition metal ions and / or rare earth metal ions and / or main group metal ions and / or their complexes. The complementary ligand functional groups include pyridinyl and / or bipyridinyl and / or o-phenanthroline and / or carboxyl and / or phosphate and / or aminocarboxylic acid ligands and / or histidine tags. The functional groups of the π-system include pyrene and / or perylene imide and / or porphyrin and / or phthalocyanine and / or tetraphenyl and / or crown ether aromatic derivatives; The hydrophobic functional groups include long-chain alkyl and / or aryl and / or perfluoroalkyl and / or polysiloxane and / or ester groups. The hydrophilic functional groups include ionic groups and / or polyether chains and / or polyol groups and / or betaine-type zwitterionic groups; The charged functional groups include quaternary ammonium salt cations and / or phosphonium salt cations and / or sulfonate anions and / or carboxylate anions and / or phosphate anions; The host-guest recognition functional groups include cyclodextrin derivatives and / or calixarene derivatives and / or adamantyl and / or ferrocene and / or specific organic ammonium salts; The hydrogen bond donor functional groups include amino and / or amide and / or urea and / or carboxylic acid and / or phenolic hydroxyl groups; The hydrogen bond acceptor functional groups include carbonyl and / or ether and / or ester and / or pyridine nitrogen and / or sulfonyl groups.

[0041] Two-dimensional molecular preassemblies The two-dimensional molecular pre-assembly is prepared by the method described in any one of claims 13 to 25; The two-dimensional molecular pre-assembly has at least one reactive first-class functional group and at least one reactive second-class functional group.

[0042] As a preferred option The thickness of the two-dimensional molecular pre-assembly is less than twice the thickness of the two-dimensional polymer molecule.

[0043] This invention is completely different from any existing two-dimensional polymer monolayer film products, i.e., methods for constructing and preparing two-dimensional molecular assembly films. Existing methods are almost all based on the controlled assembly and bonding of non-polymer monomer molecules to form two-dimensional molecular assemblies. However, due to the characteristics of monomer molecule polymerization and growth, the products are very likely to form three-dimensional microstructures, or introduce defects, or exhibit stacking, etc. Hereinafter, such existing methods are all monomer raw material methods.

[0044] This is based on a great many reasons.

[0045] Firstly, the existing nucleation and growth mechanisms of the monomer-based method cannot achieve the expected mononuclear growth. On most surfaces, the growth of two-dimensional crystals typically does not begin with a single nucleus and expand outwards perfectly. Instead, numerous nucleation events occur simultaneously at different locations on the surface. When these independently grown crystals (domains) meet, they cannot seamlessly merge due to slight deviations in their lattice orientations. Grain boundaries arise as a result. The larger the crystal, the more initial domains need to be merged (or the longer the growth time of a single domain, the greater the possibility of introducing defects), resulting in more grain boundaries and defects. To obtain large single crystals, it is necessary to strictly control the nucleation density (to a very small number of nuclei) and allow monomers to be added slowly and orderly to the nucleus edges under optimal conditions. This requires near-perfect thermodynamic equilibrium conditions, which are extremely difficult to achieve and maintain experimentally. Any perturbation (such as temperature fluctuations, impurities, or substrate defects) can induce new nucleation or growth defects.

[0046] Secondly, during the diffusion process, as the crystal edge moves away from the nucleation center at the interface of two-dimensional polymerization, monomer molecules need to diffuse a longer distance to reach the growth front. In the diffusion path, monomers may be captured by defects, misattach, or undergo non-ideal reactions before reaching the correct position, resulting in defects. At the same time, monomers are required to form highly coordinated covalent bonds on the two-dimensional plane. As the reaction area expands, ensuring synchronous and isotropic reactions at all sites becomes extremely difficult. A tiny step, scratch, or adsorbed impurity atom on the substrate may only be a local defect for a small crystal, but for a large crystal attempting to overcome these obstacles, these defects will become obstacles that crystal growth must bypass or forcibly overcome, leading to the generation of dislocations, grain boundaries, or cracks, which seriously disrupts long-range order.

[0047] Thirdly, regarding stress and lattice, there may be a mismatch in lattice constants between the two-dimensional crystal and the substrate during monomer growth, or between different regions within the crystal. For small crystal domains, this stress can be partially released through edge deformation. However, as the crystal size increases, the accumulated elastic strain energy will increase exponentially. When the accumulated stress exceeds the strength limit of the thin film, it will be suddenly released through the formation of wrinkles, cracks, or peeling from the substrate. This directly destroys the continuity, flatness, and crystal integrity of the thin film. Large-size thin films are more prone to this macroscopic failure.

[0048] Furthermore, this challenge also exists in areas such as mass transfer and heat management, and long-range order control.

[0049] However, due to the fundamental change in the underlying logic of constructing two-dimensional molecular assemblies (films) and the primary raw materials of this invention, and the introduction of diverse and selectable connectors, all the above problems can be fully solved. For example... Figure 1The assembly process shown involves the saturated or unsaturated assembly of two-dimensional polymer molecules under the action of the linker, resulting in a monolayer assembly or pre-assembly. The pre-assembly can be further assembled and combined to transform into a monolayer assembly.

[0050] In terms of nucleation and growth, since the primary raw material of this invention is not a non-polymer monomer molecule, but a two-dimensional polymer molecule that has already formed polymers (the two-dimensional polymer molecules claimed in this invention include standard planar two-dimensional polymer molecules, as well as some approximately two-dimensional quasi-two-dimensional polymer molecules, i.e. polymer molecules whose thickness is less than twice the thickness of their monomer molecules before polymerization), it can also be regarded as a two-dimensional crystal domain, which is a number of independent, small-sized two-dimensional polymer sheets that may have edge functional groups. These sheets can be prepared in large quantities by existing methods. Then, the introduced linkers are used as molecular-scale "stitching lines" or "interface adhesives" to connect, splice, and integrate these pre-formed crystal domains in a two-dimensional plane. This reduces the extreme control of the macroscopic growth dynamics of the entire system to the control of local chemical reactions at the edges of the crystal domains. With reasonable molecular design (linkers) and mature and suitable interface assembly technology, the difficulty is greatly reduced, and the controllability and universality are significantly enhanced. This is because when two two-dimensional polymer molecular sheets with their edge "type II functional groups" approach each other but with slight misalignment, the core (P) of the connector provides structural support, and its connecting arms (R') provide the necessary spatial freedom and orientation, allowing the type I functional groups (R1) at both ends of the connector to "reach" and match the functional groups at the edges of the two sheets. The connector, like a "chemical rivet," covalently locks the two sheets together. This bond strength is sufficient to stabilize a small-angle tilted grain boundary that might be defined as a "defect" in direct growth. Furthermore, through the synergistic effect of multiple connectors, the two sheets can be "pulled" into a more coherent arrangement, forming a high-quality, large-area, continuous two-dimensional polymer arrangement, ultimately resulting in a saturated two-dimensional molecular assembly. In this invention, saturation is defined as macroscopic and industrial-level saturation, meaning that in the reaction system, the reaction has completely stopped, and further changes are almost undetectable, but there may still be unreacted active sites in the system. This is due to... Due to steric hindrance, kinetic traps, or equilibrium constraints, unsaturated intermediate two-dimensional molecular pre-assemblies may be obtained. These two-dimensional molecular pre-assemblies can be used as preforms or regarded as larger, special "two-dimensional polymer molecules" with connectors. These intermediates have no direct significance in the laboratory, but in the industrial field, they can improve the industrial efficiency of the present invention. For example, if some connections need to be completed through more special photochemical assembly, they can be completed in advance in the factory or laboratory. After forming the two-dimensional molecular pre-assemblies, simpler assembly operations such as thermochemical treatment or interface assembly can be added on the industrial site, thereby reducing the construction cost on the industrial site and improving the construction efficiency on the site.

[0051] Furthermore, the bonding between the linker of this invention and the primary raw material two-dimensional polymer molecules is less affected by the perfect equilibrium of the system because it transforms into a diffusion-controlled interfacial reaction. The reaction can be localized, and the degree of controllability is significantly increased. Even if individual linking reactions fail or the initial arrangement of the layers is imperfect, subsequent linker molecules can continue to "fill in the gaps." The entire process has the potential for dynamic adjustment and self-repair, which is not possible with direct growth. Moreover, due to the unique modular design of the linker of this invention, its core is responsible for controlling the geometry (e.g., linear, triangular, square, etc.) and physical properties (e.g., rigidity, conjugation, etc.) of the linker, which determines the topology of the final assembly. The first type of functional group is responsible for the physical / chemical compatibility with the edge of a specific two-dimensional polymer. By changing the first type of functional group (e.g., amino, azide, pyridine, etc.), the same core P can be used to connect two-dimensional materials with completely different surface chemistry, forming a "linker toolbox." When faced with a completely new two-dimensional polymer, researchers do not need to explore growth conditions from scratch. They only need to select a geometrically matching core and a chemically matching functional group from the toolbox to combine them into an effective linker to start assembly.

[0052] In other words, this invention is a highly original molecular design that transforms the thermodynamic / kinetic control problem of "crystal growth" into the synthetic chemistry and interface science problem of "modular molecular stitching," and effectively solves the problem.

[0053] Regarding diffusion, monomers need to diffuse over long distances to the growth front, where they are easily captured or subject to side reactions, leading to internal crystal defects. This requires countless reaction sites on a two-dimensional plane to form high-energy covalent bonds synchronously and at the same rate. Any uneven rate will result in stress, dislocation, or termination, and any microscopic substrate defects will be "magnified" into macroscopic structural defects (such as dislocations and cracks) as the crystal expands, destroying the overall integrity. However, this invention transforms the "monomer transport problem," which requires millimeter-level diffusion and is extremely difficult to control, into a "interface connection problem" with nanoscale positioning and well-defined chemical reactions. The diffusion path is greatly shortened, the probability of side reactions drops sharply, and fast, efficient reactions with few byproducts can be selected (such as alkyne-azide cycloaddition), ensuring efficient and stable connection. The connection reaction can start from several contact points and gradually extend, without requiring all connection points to react simultaneously. The connecting arms R' of some connectors (if present) also provide flexible arms that can tolerate temporary mismatches and dynamically adjust during the reaction. The "fragile thermodynamic equilibrium that must be maintained globally in real time" is replaced with "a stable chemical reaction that can be initiated locally on demand." The requirement for synergy is reduced from "global instantaneous" to "local sequential," resulting in a qualitative leap in controllability. Furthermore, the growth front of traditional monomeric molecular crystals must extend close to the substrate. Scratches and steps on the substrate are insurmountable obstacles; the crystal must twist itself (generating dislocations) or re-nucleate (generating grain boundaries) to "climb over" them. However, when assembled using the connector of this invention, the two-dimensional polymer sheets and connectors are mainly controlled by interfacial tension and intermolecular forces, greatly reducing the influence of the substrate. Even if there is a height difference or twist at the joint of the two sheets (similar to the residual effects of substrate steps), the connector (especially with a flexible R' arm design) can act as a stress buffer and geometric adapter. By firmly connecting the two sheets through covalent bonds, this "defect" is absorbed within a flexible molecular node, preventing it from propagating into cracks or dislocation lines that penetrate the entire crystal.

[0054] Regarding the effects of stress and lattice, the primary raw material of this invention is a pre-synthesized two-dimensional polymer sheet, which can be regarded as an independent, stress-relaxed "rigid island". Its internal stress is fixed during the synthesis stage and is small in size, insufficient to cause self-fracture. The connector does not change the intrinsic stress state inside these "islands". It reduces the challenge of large-scale preparation from "growing a stress-free large single crystal" to "synthesizing many low-stress small sheets", which is much easier in terms of process. When adjacent two-dimensional polymer sheets undergo small relative displacement (tension, shear or rotation) due to thermal expansion or external load, the flexible or semi-rigid structure or R' arm can absorb this deformation energy through its conformational changes (rotation, bending, stretching), while the rigid structure or R' arm can directly eliminate this small relative displacement by binding and pulling the two-dimensional polymer molecular sheets through strong bond energy. The stress is no longer transmitted and accumulated in the rigid network, but is dissipated and buffered by the connector, preventing micro-strain from condensing into macro-cracks. The final product, the two-dimensional molecular assembly, is only constrained by mild interfacial tension. Once assembled, it can be gently transferred to any target substrate.

[0055] By introducing the modular connector designed in this invention, almost all the problems existing in the construction process of traditional two-dimensional monolayer thin film products can be effectively solved. At the same time, with the advancement of technology, it can also adapt to the assembly of new two-dimensional polymer molecules for thin film construction.

[0056] In response, the present invention provides the following reference design table, which enables modular design of linker molecules corresponding to the selected primary raw material (two-dimensional polymer molecule) and its contained second type of functional groups.

[0057] Table 1: Primary Functional Group Matching Table Based on Table 1 above, further detailed classification is performed, resulting in the following table.

[0058] Table 2: Matching Table of Secondary Functional Groups Based on Table 2 above, we further categorize the data in detail to obtain the following table.

[0059] Table 3: Examples of Matching References for Some Tertiary (Specific) Functional Groups Based on Tables 1-3 above, a verified and effective selection table of the first type of functional groups required by the linker based on the second type of functional group has been provided. Based on Tables 1-3 above, technicians can easily reproduce the assembly and bonding of specific two-dimensional polymer molecules, and can make the required selection of the first type of functional groups in the modular linker molecules, ensuring the diversity of selection. For example, when the second type of functional group on the edge of the target two-dimensional polymer molecule is an amino group, the first type of functional group can be selected as succinimidyl ester group and / or aldehyde group and / or isocyanate group and / or epoxy group, all of which can carry out electrophilic-nucleophilic reactions. As another example, when the second type of functional group is an azide group, an alkyne group can be selected as the first type of functional group. The selectable reaction paths include click chemistry, cyclization reaction and thermal initiation reaction, etc., with a high degree of freedom in overall design and use.

[0060] Based on the above sequence, for the correspondence results of the first type of functional groups and the second type of functional groups in the same sequence, the present invention also provides the following assembly and bonding method matching table, giving the selection of assembly and bonding methods that can be used after realizing the functional group correspondence.

[0061] Table 4: Examples of Matching and Comparison of Assembly and Combination Methods After designing the linker by matching the sequence selection in Table 3 with the first type of functional group that matches the second type of functional group, the actual assembly process can refer to the preferred assembly method in Table 4, but it is not completely limited to Table 4. All the methods in Table 4 have been verified and have effectiveness and reliability.

[0062] In linkers, besides the decisive role played by the first type of functional groups, the key characteristics of two-dimensional polymer molecules can be used to determine in advance whether linker arms need to be designed and what type of linker arms should be designed, thereby improving the design efficiency and effectiveness of linkers. See the table below.

[0063] Table 5: Examples of the Necessity of Connector Arm Design for Connectors Meanwhile, as the most critical and indispensable part of the linker, the selection of the molecular core of the linker molecule is also very important and therefore requires design. Since the selection of the molecular core is structure-first, the geometric type of the core can be determined first based on the macroscopic assembly goals, and then the edge chemistry can be matched to ensure compatibility with type I functional groups. Based on the matching comparison table of type I and type II functional groups in Table 3, specific examples of linker molecular core matching selection can be seen in the table below.

[0064] Table 6: Examples of matching selection for linker molecular cores Therefore, based on the examples in Tables 1 to 6 above, the linker molecules claimed by this invention actually include both optional design schemes and final design results. Of course, the above examples do not limit the design directions and choices, and therefore should not be used to directly limit the scope of protection of this invention; only experimentally verified preferred choices are shown. Furthermore, the molecular core of the linker can, in some cases, be directly selected as an extremely small molecular core, such as a methylene group, which directly connects two type-1 functional groups to form an extremely small linker molecule.

[0065] Based on the above, it can be clearly understood that the linker molecule provided by this invention is actually an indeterminate molecule that can be synthesized or selected based on design, but it can achieve a specific function, namely, it can reassemble two-dimensional polymer molecules and the assembly is restricted to a "plane". This "plane" means that the two-dimensional polymer molecules will not stack and / or connect in the Z-axis direction (thickness direction) under the action of the linker of this invention, but will be assembled and bonded basically within the plane formed by the XY axis directions of the sheet-like two-dimensional polymer molecules. The assembly scope claimed by this invention is limited to "assembly in a single-layer space", that is, controlling the thickness of the two-dimensional molecular assembly and / or pre-assembly to be <2 times the thickness of the two-dimensional polymer molecules. This is because, for the technical solution of this invention, firstly, some Two-dimensional polymer molecules with special spatial configurations may form certain misalignments along the Z-axis due to molecular volume effects, but they can still generally assemble and combine along the XY-axis. In this case, by designing and / or synthesizing and / or selecting appropriate linkers, it is possible to more effectively constrain the assemblies and / or pre-assemblies to maintain the structural characteristics of two-dimensional sheets. The restriction on the assemblies and / or pre-assemblies is equivalent to further screening out linkers with better performance. Secondly, the linkers of this invention can also be used to assemble and construct composite sheet two-dimensional polymer assemblies. For example, if two different sheet two-dimensional polymer molecules are selected for assembly and combination, the resulting assemblies and / or pre-assemblies cannot meet the absolute description of "two-dimensional" and / or "planar".

[0066] The design and / or synthesis and / or screening of linker molecules are absolutely crucial to ensuring the effectiveness of the linkers in this invention. The limiting conditions of this invention are essentially the judgment of the design and / or synthesis and / or screening results. If the condition that "the linker and the two-dimensional polymer combine in any ratio to form a layered polymer with a thickness less than twice the thickness of a single two-dimensional polymer" is met, then it can be determined that the design and / or synthesis and / or screening results of the linker are correct, the linker is effective, and the result meets expectations, assembling the two-dimensional polymer into a larger two-dimensional assembly while maintaining its planar structural characteristics.

[0067] Furthermore, the linkage claimed in this invention binds to the two-dimensional polymer molecule via physical bonding and / or chemical bonding, and at least one linker group contains at least one first-class functional group capable of chemically bonding with the two-dimensional polymer. This is based on earlier research results such as US20210002426A1 and US20250136759A1, which showed that the invention could effectively form two-dimensional assemblies. However, these assemblies were based on weak forces such as hydrogen bonds, resulting in limited stability of the assembled products, especially monolayer films, which were very susceptible to breakage due to physical disturbances. This invention differs from earlier research results by innovatively introducing a linker, which, through chemical bonding... This invention significantly improves the stability of assembly and bonding, and effectively expands the types of two-dimensional polymer molecules that can be assembled. For example, many two-dimensional polymer molecules lack functional groups at their edges that can be physically bonded by hydrogen bonds, and some may be limited by molecular volume effects, preventing the breakdown of hydrogen bonds and the formation of physical bonds. The linker of this invention largely solves this problem, enabling the assembly and bonding of any number of types of two-dimensional polymer molecules with any edge functional groups. By designing suitable molecular cores, connecting arms, and compatible first-class functional groups, it ensures that the first-class functional groups have sufficiently long "arm span" contact and good bondability, achieving bonding connections. Compared with earlier research results, the linker of this invention, in addition to introducing chemically bondable first-class functional groups, can selectively retain physically bonded first-class functional groups. These physically bonded first-class functional groups also help the linker to quickly locate and align, allowing the linker to contact the two-dimensional polymer molecules more quickly, and, depending on the situation, can promote the alignment of the linker and the two-dimensional polymer molecules.

[0068] like Figure 2 As shown, for ease of description and understanding, some two-dimensional polymer molecules with special structures are represented by geometric shapes. Assume there are two types of two-dimensional polymer molecules, A and B, i.e. Figure 2The 2D Polymer (A) and 2D Polymer (B) have second-class functional groups R2 and R2' attached to their upper edges, respectively. R2 and R2' are nucleophilic and electrophilic functional groups, respectively. Figure 2 As shown, the two cannot bond due to molecular volume effects. However, after introducing the linker R1-P-R1', the first-class functional groups R1 and R1' attached to it are electrophilic and nucleophilic functional groups, respectively, which can form R2-R1 and R2'-R1' connections. This solves the problem of excessively large inter-functional group spacing due to molecular volume effects, preventing bonding. Furthermore, in cases where the volume effect is more severe, a linker arm R can be selectively introduced to further extend the connection distance, thereby achieving the connection and assembly of two-dimensional polymers. And so on... Figure 4 As shown, the same 2D Polymer (A) and 2D Polymer (B) have second-type functional groups R2 and R2' attached to their upper edges, respectively. These second-type functional groups R2 and R2' are nucleophilic and electrophilic functional groups, respectively. Besides requiring a linker R1-P-R1', if the linker can also... Figure 5 The preliminary positioning of the linker with the two-dimensional polymer molecule via hydrogen bonds allows for more efficient assembly, improving the orderliness and molecular density of the assembly. However, for the technical solution of this invention, the primary consideration is still the first type of functional group capable of chemically bonding with the second type of functional group, thereby improving the stability of the two-dimensional polymer molecule assembly. Furthermore, since the technical solution of this invention allows for modular design of the linker and screening from existing chemical molecular libraries based on the design results, or using platforms such as IBM RXN or ASKCOS for synthetic route planning and synthesis, the specific applications of the linker of this invention can mostly be directly screened from existing organic molecular libraries based on the modular design results, providing a novel application path for it as a linker.

[0069] Assuming the second type of functional group on the edge of the target two-dimensional polymer molecule is an aldehyde group, then an amino group can be chosen as the first type of functional group. In this case, common diaminomethane (H2N-CH2-NH2) can be used as a linker, or common chemical raw materials such as 4,4'-diaminodiphenylmethane can be used. However, 4,4'-diaminodiphenylmethane is commonly used in the production of polyurethane and epoxy resins and is not typically used as a linker. This opens up entirely new applications for many common chemical substances, including common chemical materials such as JP83 and RG-2833 in biochemicals. Based on the selection and determination of the first type of functional groups, further determination can be made based on other characteristics of the two-dimensional polymer molecule, such as the location of the second type of functional groups, the high flatness of the overall surface morphology of the two-dimensional polymer molecule, and the steric hindrance of the edge functional groups. This allows for further determination of whether a linker arm is needed and what type of linker arm is required. Furthermore, based on the specific types and bonding forms and bond energies of the first and second type of functional groups, it can be determined whether the molecular core of the linker needs to be screened and designed. If the desired target composition cannot be obtained from existing chemical substances and raw materials, a synthetic route can be planned and synthesized using platforms such as IBM RXN or ASKCOS.

[0070] Therefore, this invention not only provides linkers, linker design / screening methods, and linker usage methods, but also essentially expands the application of many existing chemical substances and raw materials in a completely new field of microscopic molecular assembly.

[0071] The beneficial effects of this invention are: The linker of this invention is universally applicable to the assembly and bonding of almost all two-dimensional polymer molecules, constructing the required two-dimensional molecular assemblies and / or two-dimensional molecular pre-assemblies. It can also simultaneously assemble different types of two-dimensional polymer molecules to construct novel composite two-dimensional molecular assemblies and achieve functionalization. It has broad applicability, effectiveness and efficiency, and can ensure that the constructed two-dimensional molecular assemblies and / or two-dimensional molecular pre-assemblies have extremely high stability, effectively expanding the application fields of existing chemical components. Attached Figure Description

[0072] Figure 1 This is a schematic diagram of the assembly path of the present invention; Figure 2 This is a schematic diagram of a two-dimensional polymer assembly without connectors. Figure 3 Schematic diagram A of two-dimensional polymer assembly with the assistance of linkers; Figure 4 Schematic diagram B of two-dimensional polymer assembly with connector assistance; Figure 5Schematic diagram C of two-dimensional polymer assembly assisted by linkers; Figure 6 The above are the AFM characterization results of the two-dimensional polyarylamide before assembly in Example 1 of this invention; Figure 7 The AFM characterization results are as follows: The pre-assembled structure of the two-dimensional polyarylamide obtained by linker β-alanine ethyl ester in Example 1 of this invention. Figure 8 The above are the AFM characterization results of the self-assembly of two-dimensional polyarylamide in the control group of Example 1 of this invention; Figure 9 The AFM characterization results are shown for the two-dimensional polyarylamide-ethylene glycol preassembled in Example 1 of this invention. Figure 10 The AFM characterization results are as follows for the two-dimensional polyarylamide-1,4-butanediol pre-assembly in Example 1 of this invention; Figure 11 The AFM characterization results are shown for the two-dimensional polyarylamide-PEG200 pre-assembled assembly in Example 1 of this invention. Figure 12 AFM characterization results of the two-dimensional polyarylamide-hydroxyethyl methacrylate photocrosslinked preassembled in Example 1 of this invention; Figure 13 AFM characterization results of the two-dimensional polyarylamide-hydroxyethyl methacrylate thermally crosslinked preassembled in Example 1 of this invention; Figure 14 The above are the AFM characterization results of the two-dimensional polyarylamine before assembly in Example 1 of this invention; Figure 15 AFM characterization result A is the result of the pre-assembly test of the two-dimensional polyarylamine and β-alanine ethyl ester linker in Example 1 of this invention. Figure 16 The AFM characterization result B is the result of the pre-assembly test of the two-dimensional polyarylamine and β-alanine ethyl ester linker in Example 1 of this invention. Figure 17 The above are the AFM characterization results of the two-dimensional polysulfide before assembly in Example 2 of this invention; Figure 18 The AFM characterization results are as follows: In Example 2 of this invention, two-dimensional polysulfide and 1,3,5-triacryloylhexahydro-1,3,5-triazine were pre-assembled. Detailed Implementation

[0073] The present invention will be further described clearly and in detail below with reference to specific embodiments and the accompanying drawings. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below are generally only some, not all, of the embodiments of the present invention. Therefore, all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0074] Unless otherwise specified, all raw materials used in the embodiments of the present invention are commercially available or obtainable by those skilled in the art; unless otherwise specified, all methods used in the embodiments of the present invention are methods mastered by those skilled in the art.

[0075] Example 1 Based on the assembly of two-dimensional molecular assemblies from two-dimensional polyarylamides, the two-dimensional polyarylamides are first identified. Their edge functional groups are amino and / or carboxyl groups, and their second type of functional groups can be identified as amino and / or carboxyl groups. They can be identified as covalently bonded functional groups and / or physically bonded functional groups.

[0076] The first type of functional groups are screened and designed based on amino and / or carboxyl groups. Based on the selected second type of functional groups, covalently bonded functional groups and / or physically bonded functional groups can be selected. Furthermore, among the covalently bonded functional groups and / or physically bonded functional groups, nucleophilic functional groups and / or electrophilic functional groups and / or photoinitiating functional groups and / or thermally initiating functional groups can be further identified as the first type of functional groups.

[0077] Based on this, the specific first-class functional groups that can be selected include amino, ester, carboxyl, mercapto, epoxy, acrylate, methacrylate, etc. Therefore, through simple preliminary screening in the existing chemical molecular library, common and commonly used linker molecules that can be easily screened include: β-alanine ethyl ester, 8-aminooctanoic acid, cysteine, glycidyl, 2-(ethylene oxide-2-yl)ethanol, 2-hydroxyethyl acrylate and hydroxyethyl methacrylate, etc. More common and inexpensive raw materials such as ethylene glycol can also be used.

[0078] Based on the selection of the above linkers, assembly experiments were conducted on two-dimensional polyarylamides.

[0079] For example, 1,3,5-benzenetricarboxyl chloride (TMC) and melamine (MA) were mixed in a 1:1 molar ratio and dissolved in ultra-dry N-methylpyrrolidone (NMP) to prepare a pre-solution with a total concentration of 0.055 g / mL. 0.15 times the volume of the pre-solution was added to the pre-solution, and the mixture was stirred at room temperature and pressure for 48 h to obtain a two-dimensional polyarylamide paste (the target two-dimensional polymer paste). This paste was then diluted with 10 times its volume of NMP to obtain a solution, thus obtaining the target two-dimensional polyarylamide solution. A small amount of the two-dimensional polyarylamide solution was first diluted 1000 times with NMP to obtain a diluted solution. This diluted solution was then observed and photographed using a high-resolution atomic force microscope (AFM). (The sample preparation method was as follows: the diluted solution was used as the test solution, and the test solution was spin-coated onto the surface of an ultra-flat and clean silicon wafer at 1000 rpm. This sample preparation method was used for all subsequent AFM characterizations.) The results are as follows: Figure 6 As shown, the molecular diameter is typically around 20–30 nm. Subsequently, β-alanine ethyl ester was added to the two-dimensional polymer solution at a ratio of 2 mg / mL, and the mixture was stirred for 24 h to obtain a reaction solution. This reaction solution was diluted 1000 times with NMP and then spin-coated onto an ultra-clean silicon wafer surface at 1000 rpm. After drying at 80 °C to remove the solvent (at this point, aggregates of two-dimensional polymer molecules and linkers are formed, i.e., a high density of two-dimensional polymer molecules and linkers), the mixture was heated to 140 °C for thermal crosslinking for 5 min to obtain a pre-assembled body. The pre-assembled body was dissolved in NMP at a ratio of 0.5 mL / cm² silicon wafer surface area (spin-coated area) to obtain a pre-assembled body solution. Since the concentration was already extremely low at this point, no further dilution was required after sampling, and AFM characterization was performed directly. The results are as follows. Figure 7 As shown, the molecular diameter expands significantly, and assembly can be observed to begin. The molecular diameter typically reaches 40–50 nm or more. Usually, 2–3 two-dimensional polyarylamide molecules assemble and bond under the action of linkers, without any direct stacking along the thickness direction (Z-axis). In the control group experiment, the two-dimensional polyarylamide was diluted 1000 times with NMP and spin-coated onto an ultra-flat and clean silicon wafer surface at 1000 rpm. After drying at 80 °C to remove the solvent, it was heat-treated at 140 °C for 5 min to obtain the product. The product on the silicon wafer surface was then dissolved with NMP, and samples were taken undiluted for AFM characterization. The results are as follows. Figure 8As shown, no effective assembly was formed, nor was any assembly trend observed. This indicates that although the two-dimensional polyarylamide itself possesses the theoretical possibility of further assembly, its self-assembly may not be completed due to steric hindrance and diffusion limitations caused by molecular volume effects. However, under the influence of the linker β-alanine ethyl ester, this occurred significantly, forming a pre-assembled structure. Further analysis of the pre-assembled solution using 200W ultrasonic oscillation for 30 min and heating at 80 °C for 30 min, followed by characterization using the simpler and faster dynamic light scattering (DLS) method to observe its molecular diameter, compared to... Figure 7 The characterization results showed that the molecular diameter remained at 40–50 nm or higher after ultrasonic oscillation or heat treatment, indicating that it has good binding stability, far superior to the hydrogen bonding form of earlier research and development schemes.

[0080] In addition, assembly verification experiments were conducted on the remaining linker molecules selected in this example. These are shown in Table 7 below.

[0081] Table 7: Assembly test conditions and results of two-dimensional polyaramid-linker Note: Unless otherwise specified, NMP was used as the solvent for all experimental groups in Table 7. The solution concentration, spin coating conditions, redissolution, sampling, and AFM characterization processes at each stage were the same as those of the aforementioned experimental groups. Only the selection of the linker and the crosslinking conditions (i.e., the assembly method) were changed. All experiments were conducted under a nitrogen protective atmosphere. All linkers used were 2 mg / mL two-dimensional polymer solutions (unless otherwise specified in the embodiments of this invention). Characterization of thermal and mechanical stability is marked with "√", which indicates that the molecular diameter hardly changes after 30 min of ultrasonic oscillation at 200 W or heating at 80 °C for 30 min, and the mean decrease is <5%. Marking with "×" indicates that the molecular diameter changes significantly after 30 min of ultrasonic oscillation at 200 W or heating at 80 °C for 30 min, and the mean decrease is ≥5%.

[0082] As can be clearly seen from the results in the table above, the linkers screened by the method of this invention all possess the ability to assemble and bond with two-dimensional polyarylamides, and promote the further assembly of two-dimensional polyarylamides into larger sheet monolayer structures. Different linkers exhibit varying bonding abilities, but the method provided by this invention, along with the specific modularity constraints on the linkers, is sufficient to develop a large number of applications using various common chemical components as linkers for two-dimensional polymer molecular assembly. Furthermore, the resulting assemblies / pre-assemblies (in this example, all are pre-assemblies) all possess good thermal and mechanical stability.

[0083] In addition, the assembled / pre-assembled products of some experimental groups were also characterized by AFM. As shown in Figure 9, the selected linker was ethylene glycol, derived from... Figure 7 and Figure 9 Comparing the results, it is evident that both methods achieved the monolayer assembly required by this invention, although... Figure 9 The results showed that the thickness of some pre-assembled parts increased significantly, but still did not reach twice the thickness of the two-dimensional polyarylamide polymer molecules, indicating that no stacking occurred, but rather some misalignment may have occurred. This is due to factors such as the molecular volume effect of some two-dimensional polymer molecules. Figure 10 The AFM characterization results shown indicate that with the growth of the molecular core (or, if -CH=CH- is considered the molecular core, then with the introduction of the connecting arm -CH2-), the assembly effect is optimized to a certain extent while retaining the same type I functional groups, and the mislayer phenomenon is significantly suppressed. Therefore, for this invention, in addition to determining the type II functional groups of the two-dimensional polymer molecule itself and initially determining the complementary reactive functional group pairs based on Tables 1 and 2 of this invention, and selecting type I functional groups, the assembly method, connecting arms, and molecular core can also be optimized using Tables 4-6 provided in this invention. Optimization can also be achieved through conventional limited-number experiments, but this is only a further optimization of the effect. Whether or not it is optimized does not affect the achievement of the fundamental goal and effect of using the initially screened linkers based on this invention for the assembly and connection of two-dimensional polymer molecules within a monolayer. Based on the comparison between ethylene glycol and 1,4-butanediol linkers, the researchers conducted further comparative experiments, specifically using polyethylene glycol (specifically PEG200) as a linker. PEG200 also possesses the ability to act as a linker for two-dimensional polyarylamides because it contains two required type I functional groups. However, the characterization results of the pre-assembled structures obtained under the same assembly method were as follows: Figure 11As shown, it clearly produces a localized stacking phenomenon of two-dimensional polymer molecules in its thickness (i.e., height or Z-axis) direction, which is mainly due to its excessive chain length. Therefore, if a planar molecular core with symmetry, such as a planar aromatic ring structure and / or a rigid structure with a three-dimensional configuration, or even more precisely a molecular core containing a six-fold symmetry structure and / or a four-fold square symmetry structure and / or a triangular symmetry structure and / or a rhombic symmetry structure and / or a spirocyclic central structure, this phenomenon can be suppressed.

[0084] More importantly, the technical solution of this invention has been further validated by a technical model. The calculation process only selected the most preferred types of connectors commonly used in the experiment (including the reliable connectors used in Example 1 and some of Example 2), so the result obtained is the verifiable optimal result, and some simulation results have also been experimentally verified (including the remaining connectors used in Example 2), that is, the simulation data and calculation results correspond.

[0085] The first step in validating the technical model is to clarify the purpose and screening criteria of the linker. The linker must be able to enable the assembly of two-dimensional polymers within the two-dimensional space (monolithic space, where the Z-axis / height / thickness is less than twice the thickness of the two-dimensional polymer molecules to be linked) as defined in this invention, and absolutely avoid stacking. Therefore, it is necessary to first precisely define the static geometry of the linker molecules from a quantum chemical perspective.

[0086] The four most critical core parameters are the maximum size (Lmax) of the linker molecules, the radius of gyration (Rg), the end-to-end distance (Ree), and the aspect ratio (AR). These four factors are key physical quantities that affect the molecular stacking behavior.

[0087] The maximum size (Lmax) is derived from the Kohn-Sham equations in density functional theory (DFT) to obtain a DFT-optimized conformation. This method reduces the ground-state properties of multi-electron systems to electron density functionals, solving hypothetical non-interacting Kohn-Sham single-particle equations. At the theoretical levels of B3LYP (a hybrid functional incorporating gradient correction and partial exact exchange) and 6-31G(d,p) (a split valence basis set with added polarization functions for heavy atoms), the equations are solved to obtain the single-electron wavefunction, constructing the electron density. Through self-consistent field (SCF) iteration, the total energy is minimized, thus determining the equilibrium position of the atomic nucleus and obtaining the global minimum structure on the potential energy surface, thereby acquiring high-confidence geometric parameters. Subsequently, principal component analysis is performed on the atomic coordinates, and the maximum projection difference is the maximum size (Lmax).

[0088] The radius of gyration (Rg) is a classical statistical description based on the optimized quantum mechanical conformation. After obtaining the aforementioned DFT optimized conformation, the radius of gyration (Rg) can be calculated using classical mechanics formulas. The formula used... (In the formula: For the first The mass of a single particle, expressed in kg. For the first The perpendicular distance from each particle to the axis of rotation is expressed in meters (m). Indicates the first The contribution of a point mass to the rotational inertia of the axis of rotation (in kg·m²) is essentially the square root of the second moment of the molecular mass distribution, describing the statistical average of the molecular "size". It comprehensively reflects the size of the molecular core (P) and / or the extension of the connecting arms (R'), and is a key indicator for judging whether the overall molecule is "compact" or "extended".

[0089] The end-to-end distance (Ree) is, based on the purpose of this invention, a direct measurement and specification of specific coordinates within the linker molecule. In the DFT optimized conformation, it directly calculates the maximum linear spatial distance between any two type-1 functional groups. This parameter directly defines the "effective bridging length" of the linker.

[0090] Aspect ratio (AR) is a shape quantization based on the inertia tensor. Based on the optimized conformation, the inertia tensor of the molecule is calculated and diagonalized to obtain three principal axes and their corresponding moments of inertia. The aspect ratio is the ratio of the length of the longest axis [max(X,Y,Z)] to the length of the shortest axis [min(X,Y,Z)], i.e., Lmax / Lmin. This ratio is directly derived from the equilibrium geometry determined by the electronic structure of the molecule and reflects the anisotropy of molecular shape locked by quantum effects such as conjugation and steric hindrance.

[0091] Calculations and simulations have shown that to achieve stacking-free linker molecules in reality, the following conditions must be met: maximum size (Lmax) of at least 0.31 nm ≤ Lmax ≤ 2.98 nm, radius of gyration (Rg) of at least 0.20 nm ≤ Rg ≤ 1.97 nm, end-to-end distance (Ree) of at least 0.29 nm ≤ Ree ≤ 2.73 nm, and aspect ratio (AR) of at least 1.0 ≤ AR ≤ 6.0. Linker molecules within these geometric parameter ranges can generally achieve stacking-free assembly and monolayer assembly. Furthermore, when the maximum size (Lmax) meets the conditions of 0.79 nm ≤ Lmax ≤ 1.47 nm, the radius of gyration (Rg) meets the conditions of 0.51 nm ≤ Rg ≤ 1.16 nm, and the end-to-end distance (Ree) meets the conditions of 0.68 nm ≤ Ree ≤ 1.41 nm, the stacking-free effect is significantly improved. When the aspect ratio (AR) is in the nm range and the aspect ratio (AR) is in the range of 1.5 ≤ AR ≤ 3.0, the "planarity" of the assembly can be ensured to the maximum extent, that is, the thickness of the assembled / pre-assembled 2D polymer can be less than 1.25 times the thickness of the 2D polymer molecule.

[0092] The determination of the core geometric and volume parameters of the connector can effectively ensure the effectiveness of "monolayer assembly".

[0093] Furthermore, to ensure the effectiveness of the linker assembly of the present invention, it is necessary to further confirm the electronic structure and solvation parameters of the linker molecules. This is the basis for ensuring that the linker molecules have efficient reactive assembly capabilities on the basis of the first and second type functional groups forming a complementary reactive functional group pair. It mainly involves four parameters: HOMO-LUMO band gap (ΔE), solvent accessible surface area (SASA) (in aqueous system), solvation free energy (ΔGsolv) (in aqueous system), and steric hindrance (SASeff).

[0094] The HOMO-LUMO band gap (ΔE) is based on time-dependent density functional theory (TD-DFT). On the ground-state optimized structure, TD-DFT calculates the system's response to external perturbations (such as photons) by solving the linear response equation, thereby obtaining the excited-state properties. Its core formula is the Casida equation, and its matrix form is as follows: Matrix A and matrix B contain ground-state orbital information, specifically... For the "diagonal" portion of the excited state matrix, For the "coupling" part of the excited state matrix, Let n be the amplitude of the "excitation" of the nth excited state. The amplitude of the "de-excitation" of the nth excited state. Let be the energy of the nth excited state. The eigenvalues ​​are obtained by solving this equation. Thus, the excitation energy, including the first excited state, can be obtained. The energy difference (ΔE) between the HOMO and LUMO can be approximated as the lowest excitation energy under technical model verification.

[0095] Solvent-accessible surface area (SASA) is based on statistical mechanics and computational geometry. In the equilibrium trajectory of molecular dynamics simulations, a sphere with a radius of 1.4 Å (simulating a water molecule) is used as a probe, rolling along the van der Waals surface of the solute molecule. The point that the center of the probe can reach constitutes the solvent-accessible surface.

[0096] The solvation free energy (ΔGsolv) is exemplified by the SMD (density functional solvent model), which treats the solvent as a continuous medium with a specific dielectric constant ε, while the solute is located in a cavity of a defined shape.

[0097] The steric hindrance parameter (SASeff) is based on the surface analysis of functional groups according to the trajectory. In MD simulations, the total SASA is calculated, and the SASA contributed by atoms of all type I functional groups (reaction sites) in the linker molecule is also calculated separately using atomic indexing. The calculated values ​​are expressed by formula. The calculations directly quantify how easily the reaction sites are reached by the solvent (or reactant).

[0098] According to technical model calculations, among the four parameters mentioned above, when the HOMO-LUMO band gap (ΔE) satisfies ΔE≥1.5 eV, the solvent accessible surface area (SASA) satisfies 80 Å2≤SASA≤500 ​​Å2, the solvation free energy (ΔGsolv) satisfies -40kcal / mol≤ΔGsolv≤-2 kcal / mol, and the steric hindrance parameter (SASeff) satisfies SASeff≥20%, the assembly of the linker can be effectively ensured. Furthermore, the HOMO-LUMO band gap (ΔE) can be adjusted according to requirements. For example, if high assembly stability and good thermal and optical / electrical stability are required, a linker with a HOMO-LUMO band gap (ΔE) ≥5.0 eV can be selected. However, if some assembled / pre-assembled products require certain photochemical and / or electrochemical activities, a linker with a band gap of 2.2 eV≤ΔE≤3.0 eV is preferred.

[0099] Furthermore, it can assist in optimizing the selection of linkers based on conformational and dynamic characteristic parameters. This improves the performance of assemblies / pre-assemblies composed of linkers and two-dimensional polymer molecules to a certain extent. The main parameters include the dominant conformational energy difference (ΔEconf) and the rotatable bond ratio. The dominant conformational energy difference (ΔEconf) directly determines the Boltzmann probability of a molecule deviating from its most stable conformation at a given temperature (kBT), and is an important criterion for judging the "conformational rigidity" of a molecule. The rotatable bond ratio, verified through molecular topological structure analysis and dynamics, is a simplified proxy variable for molecular conformational entropy. Selecting linkers with a dominant conformational energy difference (ΔEconf) ≥ 12 kcal / mol can improve the crystallinity of assemblies / pre-assemblies, while selecting linkers with 3 kcal / mol ≤ ΔEconf ≤ 10 kcal / mol can improve the toughness and adaptability to rough interfaces of assemblies / pre-assemblies. The proportion of rotatable keys needs to be ≤30%. On this basis, when the proportion of rotatable keys in the connector is ≤5%, the orderliness and rigidity of the assembly / pre-assembly can be optimized. When the proportion of rotatable keys in the connector is between 18% and 22%, the toughness of the assembly / pre-assembly can be optimized.

[0100] Further as Figure 12 and Figure 13 The images shown are all assembly results of hydroxyethyl methacrylate linkers, among which... Figure 12 This is an intralayer crosslinking assembly product obtained by adding 2 wt% photoinitiator (Irgacure 907) and irradiating with 310 nm ultraviolet light for 1 min. Figure 13The intralayer crosslinking assembly products obtained by thermal crosslinking at 100℃ for 10 min are all pre-assembled bodies. A comparison reveals that the same combination of two-dimensional polymer-linkers can be used under the same parameters as any existing similar reaction or assembly methods, based on the first and second functional groups. Both methods can produce effective monolayer intralayer assembly, yielding the desired monolayer assemblies / pre-assembled bodies without additional creative effort. The basic assembly effect is achieved and effectively guaranteed; the main difference lies in the assembly efficiency. However, based on this, the present invention also provides the example table shown in Table 4 above, which allows for faster and more efficient screening of assembly methods. Furthermore, by employing any one or more optional assembly methods, such as the experimental group that “adds 2 wt% photoinitiator (Irgacure 907), irradiates with 310nm ultraviolet light for 1 min, and then performs thermal crosslinking at 100℃ for 30 min”, it can be assembled to the micrometer level, and still has not reached the assembly limit. Essentially, it can be grown to the micrometer level or even larger millimeter macroscopic level by any effective method that can promote the reaction of the first and second type functional groups, as long as the assembly time is sufficient. Moreover, due to the presence of the linker, its growth has special characteristics, and the size growth rate will show an exponential growth, so that any choice of assembly method can have a certain degree of high efficiency.

[0101] Based on the above, actual two-dimensional polyarylamines and two-dimensional polyarylamides share certain similarities, both using aromatic diamines as monomers. However, the types of edge functional groups (i.e., second-order functional groups) they contain are not entirely the same. The two-dimensional polyarylamine used in this embodiment was prepared in the laboratory using existing processes without end-capping. Unless otherwise specified, its edge second-order functional groups are all amino and aldehyde groups, with amino being the predominant. Therefore, some linkers used in actual two-dimensional polyarylamides can also be directly applied to two-dimensional polyarylamines. Thus, linkers suitable for two-dimensional polyarylamines were selected from those used in Table 7 and subjected to the same assembly verification experiments, as shown in Table 8 below.

[0102] Table 8: Assembly test conditions and results of two-dimensional polyarylamine-linker Note: The assembly method only describes the crosslinking process (assembly method); the rest is the same as the aforementioned two-dimensional polyarylamide group, such as concentration, spin-coating method, dilution degree, and AFM characterization. Before assembly, the molecular diameter of the two-dimensional polyarylamide raw material was characterized. The characterization results showed that its molecular diameter was approximately 15–20 nm. The AFM characterization results are as follows: Figure 14As shown; the markings for characterizing thermal stability and mechanical stability are “√”, which means that the molecular diameter hardly changes after 30 min of ultrasonic oscillation at 200W or heating at 80℃ for 30 min, and the mean decrease is <5%; the markings are “×”, which means that the molecular diameter changes significantly after 30 min of ultrasonic oscillation at 200W or heating at 80℃ for 30 min, and the mean decrease is ≥5%.

[0103] The characterization results show that the same linker can be used on different two-dimensional polymer molecules through the same or similar mechanisms of action.

[0104] The results in Tables 7 and 8 clearly demonstrate that the technical solution of this invention exhibits extremely high reliability and effectiveness in the design and screening of linkers. The selected linkers can be directly used to further assemble two-dimensional polymers into larger-area monolayer assemblies / pre-assemblies. Furthermore, multiple options are available for each two-dimensional polymer. The optimal linker can be selected by comprehensively considering factors such as specific usage effects, usage costs, and portability (e.g., specific construction conditions). Although the optimal linker cannot be directly screened, this invention enables rapid and high-throughput screening of usable linkers, achieving a technological breakthrough from zero to one. It also significantly expands the application prospects of existing chemical components in this field, broadening its application areas. Even if a novel, undocumented two-dimensional polymer material is successfully synthesized, this invention's technical solution can quickly adapt and reassemble it. Moreover, the same linker component is universally applicable to similar or related two-dimensional polymers, which can significantly reduce the screening cost of linkers for similar two-dimensional polymer molecules.

[0105] On the other hand, β-alanine ethyl ester linkers were also used in assembly experiments for two-dimensional polyarylamines. As mentioned above, the second type of functional groups in two-dimensional polyarylamines are mainly amino and aldehyde groups, while the first type of functional groups contained in the β-alanine ethyl ester linker are amino and ester groups. From the perspective of functional group matching, both the first and second type of functional groups are covalently bonded functional groups and have matching properties. Further analysis of the second type of functional groups revealed that the aldehyde group is an electrophilic functional group, and the amino group is a nucleophilic functional group. This means the linker needs to possess a nucleophilic functional group as a first-type functional group to form a complementary reactive functional group pair with the aldehyde group, and / or possess an electrophilic functional group as a first-type functional group to form a complementary reactive functional group pair with the amino group. Furthermore, the number of first-type functional groups must be at least two. The selected β-alanine ethyl ester contains an amino group as a first-type functional group to form a complementary reactive functional group pair with the aldehyde group. The ester group, as a first-type functional group, can also form a complementary reactive functional group pair with the amino group. Therefore, theoretically, it can also serve as a linker for assembling two-dimensional polyarylamines. Assembly experiments were conducted using the assembly conditions of "140 ℃ thermal crosslinking for 10 min." The assembly results are as follows... Figure 15As shown, assembly did indeed occur. However, assembly experiments were also conducted on two-dimensional polyarylates obtained from different sources (commercially available). These polyarylates contained only amino groups as their second-class functional groups. Therefore, when β-alanine ethyl ester was used as a linker, only one complementary reactive functional group pair was formed. This can also be considered as β-alanine ethyl ester containing only one first-class functional group. According to the standards of this invention, it cannot be used as a linker. The same assembly experiment was conducted under the condition of "thermal crosslinking at 140 °C for 10 min," and the assembly results are as follows. Figure 16 As shown, assembly indeed no longer occurs, and pre-assembled components cannot be obtained. Therefore, when determining the second type of functional groups of two-dimensional polymer molecules, i.e., active functional groups located at the ends and / or edges of the two-dimensional polymer molecules, in-depth characterization can be performed to improve the accuracy of linker screening. Alternatively, a universality-based determination can be used, i.e., selecting active functional groups that are necessarily present at the ends and / or edges of the two-dimensional polymer molecules as the second type of functional groups for universal linker screening.

[0106] Example 2 Based on the experimental results of Example 1, this example selects ten existing two-dimensional polymer materials for universality and effectiveness verification tests. In this example, the amount of linker used in each experimental group is 0.5 mg / mg of the corresponding two-dimensional polymer. Characterization of thermal and mechanical stability is marked with "√", indicating that the molecular diameter hardly changes after 30 min of ultrasonic oscillation at 200W or 30 min of heating at 80℃, with a mean decrease of <5%; marked with "×", indicating that the molecular diameter changes significantly after 30 min of ultrasonic oscillation at 200W or 30 min of heating at 80℃, with a mean decrease of ≥5%. After macroscopic film formation in some experimental groups, samples were randomly cut. The details are as follows.

[0107] Two-dimensional polymer components: two-dimensional borate covalent organic frameworks (2D BECOFs).

[0108] AFM characterization of raw materials: diameter: 400–600 nm.

[0109] Type II functional groups: borate group and / or catechol group.

[0110] The specific connector selection, assembly method, and assembly results are shown in Table 9 below.

[0111] Table 9: Assembly Tests and Results of 2D BECOFs In the table: with The marker is the connector selected through the verification model described in Example 1.

[0112] Two-dimensional polymer components: two-dimensional imine covalent organic framework TpPa-1.

[0113] AFM characterization of raw materials: diameter: 120–150 nm.

[0114] Type II functional groups: aldehyde and / or amino groups.

[0115] The specific connector selection, assembly method, and assembly results are shown in Table 10 below.

[0116] Table 10: Assembly Test and Results of TpPa-1 In the table: with The marker is the connector selected through the verification model described in Example 1.

[0117] Two-dimensional polymer component: two-dimensional polyimide.

[0118] AFM characterization of raw materials: diameter: 30–40 nm.

[0119] Type II functional groups: carboxyl and / or amino groups.

[0120] The specific connector selection, assembly method, and assembly results are shown in Table 11 below.

[0121] Table 11: Assembly Tests and Results of Two-Dimensional Polyimide In the table: with The marker is the connector selected through the verification model described in Example 1.

[0122] Two-dimensional polymer composition: two-dimensional polysulfide; AFM characterization results before assembly are as follows: Figure 17 As shown.

[0123] AFM characterization of raw materials: diameter: 20–30 nm.

[0124] Type II functional groups: thiol and / or vinyl groups.

[0125] The specific connector selection, assembly method, and assembly results are shown in Table 12 below.

[0126] Table 12: Assembly test and results of two-dimensional polysulfides In the table: with The marker is the linker selected through the technical verification model described in Example 1. The AFM characterization results of the 1,3,5-triacryloylhexahydro-1,3,5-triazine and two-dimensional polysulfide pre-assembled products are as follows: Figure 18 As shown.

[0127] Two-dimensional polymer composition: Zn-TCPP.

[0128] AFM characterization of raw materials: diameter: 200–300 nm.

[0129] Type II functional groups: unsaturated zinc ions and / or carboxyl groups.

[0130] The specific connector selection, assembly method, and assembly results are shown in Table 13 below.

[0131] Table 13: Assembly test and results of Zn-TCPP Two-dimensional polymer component: two-dimensional polyetherketone.

[0132] AFM characterization of raw materials: diameter: 20–30 nm.

[0133] Type II functional groups: fluorine and / or chlorine and / or phenolic groups.

[0134] The specific connector selection, assembly method, and assembly results are shown in Table 14 below.

[0135] Table 14: Assembly Test and Results of Two-Dimensional Polyetherketone The above experiments and characterization results clearly demonstrate that the linker claimed in this invention is consistent with theoretical and practical results, and can greatly expand the industrial application potential of all existing chemical substances, enabling modular assembly of monolayer assemblies / pre-assemblies. It has enormous research value and great industrialization prospects in two-dimensional molecular assembly technology.

[0136] Structurally: The linker described in this invention is a molecule comprising a linker molecular core and at least one linker group, as shown in Formula 1. Formula 1: ; In Equation 1: P is the core of the linker molecule and it is an organic group with a valence state ≥1; R is the linker group; x is the number of types of linker groups and x≥1; y is the total number of linker groups and y≥1. The linking group includes at least one type-first functional group that can bind to a two-dimensional polymer; The linker molecule contains at least two type I functional groups; In terms of functionality: The bonding of the linker to the two-dimensional polymer according to the present invention includes physical bonding and / or chemical bonding, and at least one linker group contains at least one first type of functional group that can be chemically bonded to the two-dimensional polymer; The connectors of the present invention are combined with two-dimensional polymers in any number to form a layered polymer, and the thickness of the layered polymer is less than twice the thickness of a single two-dimensional polymer.

[0137] By ensuring that the selected linker molecules meet the above structural and functional requirements, it can be guaranteed that the selected linker molecules can assemble and combine with two-dimensional polymer molecules in any ratio to form monolayer assemblies / pre-assembled polymers. Furthermore, if more precise and rapid selection and matching of linkers for target two-dimensional polymer molecules is required, the contents of Tables 1 and 2 described in this invention can be referenced, and / or the total of 10 linker parameters derived from the technical verification model described in Example 1 of this invention can be used as a reference.

Claims

1. A two-dimensional polymer linker, characterized in that, The linker is a molecule comprising a linker molecular core and at least one linker group; The general molecular structure of the linker is shown in Formula 1 below: Formula 1: ; In Equation 1: P is the core of the linker molecule and it is an organic group with a valence state ≥1; R is the linker group; x is the number of types of linker groups and x≥1; y is the total number of linker groups and y≥1. The linking group includes at least one type-first functional group that can bind to a two-dimensional polymer; The linker molecule contains at least two type I functional groups; The combination includes physical bonding and / or chemical bonding, and at least one linking group contains at least one first type of functional group that can be chemically bonded to a two-dimensional polymer; The connectors are combined with any number of two-dimensional polymers to form a layered polymer, and the thickness of the layered polymer is less than twice the thickness of a single two-dimensional polymer.

2. The two-dimensional polymer linker according to claim 1, characterized in that, The chemical bonds have a bond energy ≥ 60 kJ / mol.

3. The two-dimensional polymer linker according to claim 1 or 2, characterized in that, The physical bonding methods include hydrogen bonding and / or van der Waals force bonding and / or π-π stacking bonding and / or electrostatic bonding and / or host-guest inclusion bonding; The chemical bonding is in the form of covalent bonding and / or coordination bonding and / or ionic bonding, and includes at least covalent bonding.

4. The two-dimensional polymer linker according to claim 1, characterized in that, The general structural formula of the linking group is shown in Formula 2 and / or Formula 3 below: Formula 2: ; Formula 3: ; In Equations 2 and 3: R' is the linker arm, R1 is the first type of functional group, and a is the number of first type of functional groups in a single linker group, and a≥1; Preferably, the first type of functional group is a covalently bonded functional group and / or a coordination bonded functional group and / or a physically bonded functional group; More preferably, the covalently bonded functional groups include electrophilic functional groups and / or nucleophilic functional groups and / or click chemistry functional groups and / or cyclization functional groups and / or photoinitiation functional groups and / or thermal initiation functional groups. The coordination-bonded functional groups include metal central functional groups and / or complementary ligand functional groups; The physically bonded functional groups include π-system functional groups and / or charged functional groups and / or hydrophobic functional groups and / or hydrophilic functional groups and / or host-guest recognition functional groups and / or hydrogen bond donor functional groups and / or hydrogen bond acceptor functional groups. Preferably, the electrophilic functional groups include succinimide ester group and / or isocyanate group and / or epoxy group and / or aldehyde group and / or acyl chloride group and / or carboxylic acid group and / or maleimide group and / or vinyl sulfone group and / or haloalkyl group; The nucleophilic functional groups include amino and / or thiol and / or hydroxyl and / or hydrazide and / or hydrazide and / or carboxyl group and / or sodium alkoxide and / or thiolate group; The functional groups of the click chemistry reaction include alkynyl and / or azide and / or tetraazinyl and / or norbornenyl; The cyclization functional groups include dienes and / or hydrogen dienes; The metal central functional group includes transition metal ions and / or rare earth metal ions and / or main group metal ions and / or their complexes. The complementary ligand functional groups include carboxyl groups and / or acetylaceton groups and / or benzoylmethane derivatives and / or phenoxy groups and / or alcoholoxy groups and / or amino groups and / or imino groups and / or aromatic nitrogen heterocycles and / or thiols and / or thiophenol groups and / or triphenylphosphine and / or diphenylphosphine. The π-system functional groups include carbamoyl groups and / or heterocyclic aryl groups and / or their derivatives; The hydrophobic functional groups include long-chain alkyl and / or aryl and / or perfluoroalkyl and / or polysiloxane and / or ester groups. The hydrophilic functional groups include ionic groups and / or polyether chains and / or polyol groups and / or betaine-type zwitterionic groups; The charged functional groups include quaternary ammonium salt cations and / or phosphonium salt cations and / or sulfonate anions and / or carboxylate anions and / or phosphate anions; The host-guest recognition functional groups include cyclodextrin derivatives and / or calixarene derivatives and / or adamantyl and / or ferrocene and / or organic ammonium salts; The hydrogen bond donor functional groups include amino and / or amide and / or urea and / or carboxylic acid and / or phenolic hydroxyl groups; The hydrogen bond acceptor functional groups include carbonyl and / or ether and / or ester and / or pyridine nitrogen and / or sulfonyl groups.

5. The two-dimensional polymer linker according to claim 4, characterized in that, The molecular core is a molecular core containing a rigid or semi-rigid linear structure and / or a symmetrical planar aromatic ring and / or a symmetrical conjugated structure and / or a rigid structure with a three-dimensional configuration and / or a flexible segment structure. Preferred, The molecular core is a molecular core containing an aromatic alkyne structure and / or an aromatic ene structure and / or a heterocyclic straight-chain structure and / or a conjugated rod structure and / or a rigid non-conjugated rod structure and / or a triazine symmetric structure and / or a six-fold symmetric structure and / or a four-fold square symmetric structure and / or a triangular symmetric structure and / or a rhombic symmetric structure and / or a spirocyclic central structure and / or a tetrahedral central structure and / or a cage-like molecular structure and / or a basket-like molecular structure and / or a flexible alkane chain structure and / or a polyethylene glycol chain structure and / or a siloxane chain structure. More preferably, The molecular core comprises 1,4-diethynylbenzene and / or 4,4'-diaminodiphenylacetylene and / or 1,3,5-tris(4-aminophenyl)benzene and / or tetra(4-aminophenyl)porphyrin and / or 9,9'-spirodifluorene-2,7-diboronic acid and / or tetra(4-carboxyphenyl)silane and / or 1,4-phenyldiboronic acid and / or naphthalene-1,4-diboronic acid and / or 2,5-dimethoxyterephthalohydrazide and / or 2,5-bis(2-methoxyethoxy)terephthalohydrazide Formic acid hydrazide and / or 2,3,6,7,10,11-hexahydroxytriphenyl and / or 4,4'-(1,3-adamantanediyl)diphenyl and / or 9,10-anthraquinone and / or 2,7-dihydroxynaphthalene and / or 2,6-naphthoquinone and / or 1,4-dihydroxynaphthalene and / or [1,1':4',1'':4'',1'''-tetraphenyl]-3,3''',5,5'''-tetracarboxaldehyde and / or spirocyclic diol and / or spirocyclic diamine and / or 3,6-dibromo- 9,9'-spirofluorene and / or 5'-(3,5-dicarboxyphenyl)-[1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxaldehyde and / or 5',5''-bis(4-formylphenyl)-[1,1':3',1'':3'',1'''-tetraphenyl]-4,4'''-dicarboxaldehyde and / or 5-(4-formyl-[1,1-biphenyl]-4-yl)-[1,1:4,1:3,1:4, [1-Quinophenyl]-4,4-dicarboxaldehyde and / or 1,3,5-tris(4-carboxyphenyl)benzene and / or 5',5''-bis(4-formylphenyl)-2',2'',4',4'',6',6''-hexamethyl-[1,1':3',1'':3'',1'''-tetraphenyl]-4,4'''-dicarboxaldehyde and / or 4,4'-(1,2-diphenylvinyl-1,2-diyl)biphenol and / or hexa(4-aminobiphenyl)benzene.

6. The two-dimensional polymer linker according to claim 5, characterized in that, The molecular core contains a symmetrical planar aromatic ring structure and / or a rigid structure with a three-dimensional configuration; Preferably, the molecular core contains a six-fold symmetry structure and / or a four-fold square symmetry structure and / or a triangular symmetry structure and / or a rhombic symmetry structure and / or a spiral ring center structure.

7. A method for assembling a monolayer of a two-dimensional polymer, characterized in that, The method includes: Two-dimensional polymer molecules and the linkers as described in any one of claims 1 to 12 are assembled and combined once or multiple times to form a two-dimensional molecular assembly in a single-layer space through the assembly and combination of the linkers and the two-dimensional polymer. The thickness of the two-dimensional molecular assembly is less than twice the thickness of the two-dimensional polymer molecule; In the two-dimensional molecular assembly, there is at least one chemical bond between the linker and any of the two-dimensional polymer molecules it is bonded to; Preferably, the assembly and bonding methods include solvent-induced assembly and / or photochemical assembly and / or thermochemical assembly and / or electrochemical assembly and / or interface assembly and / or template-assisted assembly and / or self-assembly and / or mechanochemical assembly and / or biomolecular-assisted assembly and / or chemical vapor deposition assembly and / or epitaxial growth assembly. More preferably, The assembly methods include solvent evaporation-induced assembly and / or solvent exchange-induced assembly and / or solvent polarity modulation assembly and / or antisolvent addition-induced assembly and / or ultraviolet light-induced assembly and / or visible light-induced assembly and / or infrared light-induced assembly and / or photoisomerization-induced assembly and / or photopolymerization-induced assembly and / or heat treatment assembly and / or thermal gradient-induced assembly and / or thermally induced phase change assembly and / or thermal polymerization-induced assembly and / or DC electrochemical assembly and / or pulsed electrochemical assembly and / or AC electrochemical assembly and / or electrochemical deposition assembly and / or electrochemical polymerization assembly and / or Langmuir-Blodgett assembly and / or liquid-liquid interface assembly and / or gas-liquid interface assembly. Assembly and / or solid-liquid interface assembly and / or hard template assembly and / or soft template assembly and / or biological template assembly and / or patterned template assembly and / or molecular self-assembly and / or supramolecular self-assembly and / or block copolymer self-assembly and / or electrostatic self-assembly and / or ultrasound-assisted assembly and / or shear-induced assembly and / or ball milling-induced assembly and / or pressure-induced assembly and / or DNA origami-guided assembly and / or enzyme-catalyzed assembly and / or protein-assisted assembly and / or carbohydrate-mediated assembly and / or low-pressure CVD assembly and / or plasma-enhanced CVD assembly and / or organometallic CVD assembly and / or atomic layer deposition-assisted assembly and / or van der Waals epitaxial assembly and / or coherent epitaxial assembly and / or step-guided assembly; Preferably, the assembly and bonding methods include photochemical assembly and / or thermochemical assembly and / or interface assembly and / or template-assisted assembly; Preferably, the assembly method includes photochemical assembly and / or thermochemical assembly.

8. The method for assembling a monolayer of a two-dimensional polymer according to claim 7, characterized in that, The assembly and bonding methods include ultraviolet light-induced assembly and / or visible light-induced assembly and / or infrared light-induced assembly and / or photo-isomerization-induced assembly and / or photopolymerization-induced assembly and / or thermal treatment assembly and / or thermal gradient-induced assembly and / or thermally induced phase change-induced assembly and / or thermal polymerization-induced assembly and / or Langmuir-Blodgett assembly and / or hard template assembly and / or soft template assembly and / or biological template assembly and / or patterned template assembly; Preferably, the assembly and bonding methods include ultraviolet light-induced assembly and / or visible light-induced assembly and / or infrared light-induced assembly and / or photo-isomerization-induced assembly and / or photopolymerization-induced assembly and / or thermal treatment assembly and / or thermal gradient-induced assembly and / or thermally induced phase change-induced assembly and / or thermal polymerization-induced assembly and / or Langmuir-Blodgett assembly.

9. The method for assembling a monolayer of a two-dimensional polymer according to claim 7, characterized in that, In the two-dimensional molecular assembly, a single two-dimensional polymer molecule is connected to one or more linkers, and a single linker is connected to one or more two-dimensional polymer molecules.

10. The method for assembling a monolayer of a two-dimensional polymer according to claim 7, characterized in that, The two-dimensional polymer molecule is a polymer molecule whose thickness is less than twice the thickness of its monomer molecule before polymerization.

11. The method for assembling a monolayer of a two-dimensional polymer according to claim 7 or 10, characterized in that, The two-dimensional polymer contains a second type of functional group that binds to the linker; The second type of functional group is located at the ends and / or edges of the two-dimensional polymer molecule; Preferred, The second type of functional group is a covalently bonded functional group and / or a coordinate bonded functional group and / or a physically bonded functional group; More preferably, The covalently bonded functional groups include electrophilic functional groups and / or nucleophilic functional groups and / or click chemistry functional groups and / or photoinitiating functional groups and / or thermal initiating functional groups; The coordination-bonded functional groups include metal central functional groups and / or complementary ligand functional groups; The physically bonded functional groups include π-system functional groups and / or charged functional groups and / or hydrophobic functional groups and / or hydrophilic functional groups and / or host-guest recognition functional groups and / or hydrogen bond donor functional groups and / or hydrogen bond acceptor functional groups. More preferably, The electrophilic functional groups include succinimide ester group and / or isocyanate group and / or epoxy group and / or aldehyde group and / or acyl chloride group and / or maleimide group and / or vinyl sulfone group and / or haloalkyl group; The nucleophilic functional groups include amino and / or thiol and / or hydroxyl and / or hydrazide and / or hydrazide and / or carboxyl group and / or sodium alkoxide and / or thiolate group; The functional groups of the click chemistry reaction include alkynyl and / or azide and / or tetraazinyl and / or norbornenyl; The metal central functional group includes transition metal ions and / or rare earth metal ions and / or main group metal ions and / or their complexes. The complementary ligand functional groups include pyridinyl and / or bipyridinyl and / or o-phenanthroline and / or carboxyl and / or phosphate and / or aminocarboxylic acid ligands and / or histidine tags. The functional groups of the π-system include pyrene and / or perylene imide and / or porphyrin and / or phthalocyanine and / or tetraphenyl and / or crown ether aromatic derivatives; The hydrophobic functional groups include long-chain alkyl and / or aryl and / or perfluoroalkyl and / or polysiloxane and / or ester groups. The hydrophilic functional groups include ionic groups and / or polyether chains and / or polyol groups and / or betaine-type zwitterionic groups; The charged functional groups include quaternary ammonium salt cations and / or phosphonium salt cations and / or sulfonate anions and / or carboxylate anions and / or phosphate anions; The host-guest recognition functional groups include cyclodextrin derivatives and / or calixarene derivatives and / or adamantyl and / or ferrocene and / or specific organic ammonium salts; The hydrogen bond donor functional groups include amino and / or amide and / or urea and / or carboxylic acid and / or phenolic hydroxyl groups; The hydrogen bond acceptor functional groups include carbonyl and / or ether and / or ester and / or pyridine nitrogen and / or sulfonyl groups.

12. A two-dimensional molecular pre-assembled assembly, characterized in that, The two-dimensional molecular pre-assembly is prepared by the method described in any one of claims 7 to 11; The two-dimensional molecular pre-assembly has at least one reactive first-class functional group and at least one reactive second-class functional group; Preferred, The thickness of the two-dimensional molecular pre-assembly is less than twice the thickness of the two-dimensional polymer molecule.

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