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A polymer (;) is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via polymerization of many small molecules, known as monomers. Their consequently large molecular mass, relative to small molecule compounds, produces unique physical properties including toughness, high elasticity, viscoelasticity, and a tendency to form amorphous and semicrystalline structures rather than crystals.
In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring shape may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".
A clathrate is a chemical substance consisting of a lattice that traps or contains molecules. The word clathrate is derived from the Latin clathratus, meaning 'with bars, latticed'. Most clathrate compounds are polymeric and completely envelop the guest molecule, but in modern usage clathrates also include host–guest complexes and inclusion compounds. According to IUPAC, clathrates are inclusion compounds "in which the guest molecule is in a cage formed by the host molecule or by a lattice of host molecules." The term refers to many molecular hosts, including calixarenes and cyclodextrins and even some inorganic polymers such as zeolites.
In chemistry, a supramolecular assembly is a complex of molecules held together by noncovalent bonds. While a supramolecular assembly can be simply composed of two molecules, or a defined number of stoichiometrically interacting molecules within a quaternary complex, it is more often used to denote larger complexes composed of indefinite numbers of molecules that form sphere-, rod-, or sheet-like species. Colloids, liquid crystals, biomolecular condensates, micelles, liposomes and biological membranes are examples of supramolecular assemblies, and their realm of study is known as supramolecular chemistry. The dimensions of supramolecular assemblies can range from nanometers to micrometers. Thus they allow access to nanoscale objects using a bottom-up approach in far fewer steps than a single molecule of similar dimensions.
In chemistry, molecular Borromean rings are an example of a mechanically-interlocked molecular architecture in which three macrocycles are interlocked in such a way that breaking any macrocycle allows the others to dissociate. They are the smallest examples of Borromean rings. The synthesis of molecular Borromean rings was reported in 2004 by the group of J. Fraser Stoddart. The so-called Borromeate is made up of three interpenetrated macrocycles formed through templated self assembly as complexes of zinc.
Nanoporous materials consist of a regular organic or inorganic bulk phase in which a porous structure is present. Nanoporous materials exhibit pore diameters that are most appropriately quantified using units of nanometers. The diameter of pores in nanoporous materials is thus typically 100 nanometers or smaller. Pores may be open or closed, and pore connectivity and void fraction vary considerably, as with other porous materials. Open pores are pores that connect to the surface of the material whereas closed pores are pockets of void space within a bulk material. Open pores are useful for molecular separation techniques, adsorption, and catalysis studies. Closed pores are mainly used in thermal insulators and for structural applications.
In polymer chemistry and materials science, the term "polymer" refers to large molecules whose structure is composed of multiple repeating units. Supramolecular polymers are a new category of polymers that can potentially be used for material applications beyond the limits of conventional polymers. By definition, supramolecular polymers are polymeric arrays of monomeric units that are connected by reversible and highly directional secondary interactions–that is, non-covalent bonds. These non-covalent interactions include van der Waals interactions, hydrogen bonding, Coulomb or ionic interactions, π-π stacking, metal coordination, halogen bonding, chalcogen bonding, and host–guest interaction. The direction and strength of the interactions are precisely tuned so that the array of molecules behaves as a polymer in dilute and concentrated solution, as well as in the bulk.
Metal–organic frameworks (MOFs) are a class of porous polymers consisting of metal clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. The organic ligands included are sometimes referred to as "struts" or "linkers", one example being 1,4-benzenedicarboxylic acid (BDC).
In chemistry, a halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. Like a hydrogen bond, the result is not a formal chemical bond, but rather a strong electrostatic attraction. Mathematically, the interaction can be decomposed in two terms: one describing an electrostatic, orbital-mixing charge-transfer and another describing electron-cloud dispersion. Halogen bonds find application in supramolecular chemistry; drug design and biochemistry; crystal engineering and liquid crystals; and organic catalysis.
Zeolitic imidazolate frameworks (ZIFs) are a class of metal-organic frameworks (MOFs) that are topologically isomorphic with zeolites. ZIF glasses can be synthesized by the melt-quench method, and the first melt-quenched ZIF glass was firstly made and reported by Bennett et al. back in 2015. ZIFs are composed of tetrahedrally-coordinated transition metal ions connected by imidazolate linkers. Since the metal-imidazole-metal angle is similar to the 145° Si-O-Si angle in zeolites, ZIFs have zeolite-like topologies. As of 2010, 105 ZIF topologies have been reported in the literature. Due to their robust porosity, resistance to thermal changes, and chemical stability, ZIFs are being investigated for applications such as carbon dioxide capture.
Omar M. Yaghi is the James and Neeltje Tretter Chair Professor of Chemistry at the University of California, Berkeley, an affiliate scientist at Lawrence Berkeley National Laboratory, the Founding Director of the Berkeley Global Science Institute, and an elected member of the US National Academy of Sciences as well as the German National Academy of Sciences Leopoldina.
Covalent organic frameworks (COFs) are a class of porous polymers that form two- or three-dimensional structures through reactions between organic precursors resulting in strong, covalent bonds to afford porous, stable, and crystalline materials. COFs emerged as a field from the overarching domain of organic materials as researchers optimized both synthetic control and precursor selection. These improvements to coordination chemistry enabled non-porous and amorphous organic materials such as organic polymers to advance into the construction of porous, crystalline materials with rigid structures that granted exceptional material stability in a wide range of solvents and conditions. Through the development of reticular chemistry, precise synthetic control was achieved and resulted in ordered, nano-porous structures with highly preferential structural orientation and properties which could be synergistically enhanced and amplified. With judicious selection of COF secondary building units (SBUs), or precursors, the final structure could be predetermined, and modified with exceptional control enabling fine-tuning of emergent properties. This level of control facilitates the COF material to be designed, synthesized, and utilized in various applications, many times with metrics on scale or surpassing that of the current state-of-the-art approaches.
In crystallography, a periodic graph or crystal net is a three-dimensional periodic graph, i.e., a three-dimensional Euclidean graph whose vertices or nodes are points in three-dimensional Euclidean space, and whose edges are line segments connecting pairs of vertices, periodic in three linearly independent axial directions. There is usually an implicit assumption that the set of vertices are uniformly discrete, i.e., that there is a fixed minimum distance between any two vertices. The vertices may represent positions of atoms or complexes or clusters of atoms such as single-metal ions, molecular building blocks, or secondary building units, while each edge represents a chemical bond or a polymeric ligand.
Conjugated microporous polymers (CMPs) are a sub-class of porous materials that are related to structures such as zeolites, metal-organic frameworks, and covalent organic frameworks, but are amorphous in nature, rather than crystalline. CMPs are also a sub-class of conjugated polymers and possess many of the same properties such as conductivity, mechanical rigidity, and insolubility. CMPs are created through the linking of building blocks in a π-conjugated fashion and possess 3-D networks. Conjugation extends through the system of CMPs and lends conductive properties to CMPs. Building blocks of CMPs are attractive in that the blocks possess broad diversity in the π units that can be used and allow for tuning and optimization of the skeleton and subsequently the properties of CMPs. Most building blocks have rigid components such as alkynes that cause the microporosity. CMPs have applications in gas storage, heterogeneous catalysis, light emitting, light harvesting, and electric energy storage.
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.
Adam J. Matzger, a researcher in polymers and crystals, is the Charles G. Overberger Collegiate Professor of Chemistry at the University of Michigan.
MOF-5 or IRMOF-1 is a cubic metal–organic framework compound with the formula Zn4O(BDC)3, where BDC2− = 1,4-benzodicarboxylate (MOF-5). It was discovered by Omar M. Yaghi. MOF-5 is notable for exhibiting one of the highest surface area to volume ratios among metal–organic frameworks, at 2200 m2/cm3. Additionally, it was the first metal–organic framework studied for hydrogen gas storage.
Hexahydroxytriphenylene (HHTP) is any of a set of organic compounds consisting of a polycyclic aromatic hydrocarbon core—triphenylene—with six hydroxy group substituents attached to the rings. These compounds have found use as a component of two-dimensional polymers. The first covalent organic framework used this chemical as a monomer building block. It can be used for self-assembling metal–organic frameworks.
Carboxylate–based metal–organic frameworks are metal–organic frameworks that are based on organic molecules comprising carboxylate functional groups.
Hydrogen-bonded organic frameworks (HOFs) are a class of porous polymers formed by hydrogen bonds among molecular monomer units to afford porosity and structural flexibility. There are diverse hydrogen bonding pair choices that could be used in HOFs construction, including identical or nonidentical hydrogen bonding donors and acceptors. For organic groups acting as hydrogen bonding units, species like carboxylic acid, amide, 2,4-diaminotriazine, and imidazole, etc., are commonly used for the formation of hydrogen bonding interaction. Compared with other organic frameworks, like COF and MOF, the binding force of HOFs is relatively weaker, and the activation of HOFs is more difficult than other frameworks, while the reversibility of hydrogen bonds guarantees a high crystallinity of the materials. Though the stability and pore size expansion of HOFs has potential problems, HOFs still show strong potential for applications in different areas.
References
- ↑ Diercks, Christian S.; Yaghi, Omar M. (2017). "The atom, the molecule, and the covalent organic framework". Science . 355 (6328): eaal1585. doi:10.1126/science.aal1585.
- ↑ Li, Penghao; Ryder, Matthew R.; Stoddart, J. Fraser (2020). "Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials". Accounts of Materials Research . 1 (1): 77–87. doi:10.1021/accountsmr.0c00019.
- ↑ Furukawa, Hiroyasu; Cordova, Kyle E.; O'Keeffe, Michael; Yaghi, Omar M. (2013). "The Chemistry and Applications of Metal-Organic Frameworks". Science . 341 (6149): 1230444. doi:10.1126/science.1230444.