A two-dimensional polymer (2DP) is a sheet-like monomolecular macromolecule consisting of laterally connected repeat units with end groups along all edges. This recent definition of 2DP is based on Hermann Staudinger's polymer concept from the 1920s. According to this, covalent long chain molecules ("Makromoleküle") do exist and are composed of a sequence of linearly connected repeat units and end groups at both termini. Moving from one dimension to two offers access to surface morphologies such as increased surface area, porous membranes, and possibly in-plane pi orbital-conjugation for enhanced electronic properties. They are distinct from other families of polymers because 2D polymers can be isolated as multilayer crystals or as individual sheets. The term 2D polymer has also been used more broadly to include linear polymerizations performed at interfaces, layered non-covalent assemblies, or to irregularly cross-linked polymers confined to surfaces or layered films. 2D polymers can be organized based on these methods of linking (monomer interaction): covalently linked monomers, coordination polymers and supramolecular polymers. 2D polymers containing pores are also known as porous polymers. Topologically, 2DPs may thus be understood as structures made up from regularly tessellated regular polygons (the repeat units). Figure 1 displays the key features of a linear and a 2DP according to this definition. For usage of the term "2D polymer" in a wider sense, see "History".
Covalently-linked polymers 2DPs include the individual layers or sheets of graphite (called graphenes), MoS2, (BN)x and layered covalent organic frameworks. As required by the above definition, these sheets have a periodic internal structure. Graphene has a honeycomb lattice of carbon atoms that exhibit semiconducting properties. A potential repeat unit of graphene is a sp2-hybridized carbon atom. Individual sheets can in principle be obtained by exfoliation procedures, though in reality this is a non-trivial enterprise. Molybdenum disulfide can be produced as a sheet-like structure by exfoliation. Such sheets represent two-dimensional polymers.
Porphyrins are an additional class of conjugated, heterocyclic macrocycles. Control of monomer assembly through covalent assembly has also been demonstrated using covalent interactions with porphyrins. Upon thermal activation of porphyrin building blocks, covalent bonds form to create a conductive polymer, a versatile route for bottom-up construction of electronic circuits has been demonstrated.
COFs
Two dimensional covalent organic frameworks (COFs) are one type of microporous coordination polymer that can be fabricated as a 2DP. The dimensionality and topology of the 2D COFs result from both the shape of the monomers and the relative and dimensional orientations of their reactive groups. These materials contain desirable properties in fields of materials chemistry including thermal stability, tunable porosity, high specific surface area, and the low density of organic material. By careful selection of organic building units, long range π-orbital overlap parallel to the stacking direction of certain organic frameworks can be achieved. It is possible to synthesize COFs using both dynamic covalent and non-covalent chemistry. The kinetic approach involves a stepwise process of polymerizing pre-assembled 2D-monomer while thermodynamic control exploits reversible covalent chemistry to allow simultaneous monomer assembly and polymerization. Under thermodynamic control, bond formation and crystallization also occur simultaneously. Covalent organic frameworks formed by dynamic covalent bond formation involves chemical reactions carried out reversibly under conditions of equilibrium control. Because the formation of COFs in dynamic covalent formation occurs under thermodynamic control, product distributions depend only on the relative stabilities of the final products. Covalent assembly to form 2D COFs has been previously done using boronate esters from catechol acetonides in the presence of a lewis acid (BF3*OEt2). 2D polymerization under kinetic control relies on non-covalent interactions and monomer assembly prior to bond formation. The monomers can be held together in a pre-organized position by non-covalent interactions, such as hydrogen bonding or van der Waals.
Supramolecular polymers
Supramolecular assembly requires non-covalent interactions directing the formation of 2D polymers by relying on electrostatic interactions such as hydrogen bonding and van der Waals forces. To design artificial assemblies capable of high selectivity requires correct manipulation of energetic and stereochemical features of non-covalent forces. Some benefits of non-covalent interactions is their reversible nature and response to external factors such as temperature and concentration. The mechanism of non-covalent polymerization in supramolecular chemistry is highly dependent on the interactions during the self-assembly process. The degree of polymerization depends highly on temperature and concentration. The mechanisms may be divided into three categories: isodesmic, ring-chain, and cooperative.
One example of isodesmic associations in supramolecular aggregates is seen in Figure 7, (CA*M) cyanuric acid (CA) and melamine (M) interactions and assembly through hydrogen bonding. Hydrogen bonding has been used to guide assembly of molecules into two-dimensional networks, that can then serve as new surface templates and offer an array of pores of sufficient capacity to accommodate large guest molecules. An example of utilizing surface structures through non-covalent assembly uses adsorbed monolayers to create binding sites for target molecules through hydrogen bonding interactions. Hydrogen bonding is used to guide the assembly of two different molecules into a 2D honeycomb porous network under ultra high vacuum seen in figure 8. 2D polymers based on DNA have been reported
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