Coordination polymer

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Figure 1. An illustration of 1- 2- and 3-dimensionality. DimensionalityandCoordination.png
Figure 1. An illustration of 1- 2- and 3-dimensionality.

A coordination polymer is an inorganic or organometallic polymer structure containing metal cation centers linked by ligands. More formally a coordination polymer is a coordination compound with repeating coordination entities extending in 1, 2, or 3 dimensions. [1]


It can also be described as a polymer whose repeat units are coordination complexes. Coordination polymers contain the subclass coordination networks that are coordination compounds extending, through repeating coordination entities, in 1 dimension, but with cross-links between two or more individual chains, loops, or spiro-links, or a coordination compound extending through repeating coordination entities in 2 or 3 dimensions. A subclass of these are the metal-organic frameworks, or MOFs, that are coordination networks with organic ligands containing potential voids. [1]

Coordination polymers are relevant to many fields, having many potential applications. [2]

Coordination polymers can be classified in a number of ways according to their structure and composition. One important classification is referred to as dimensionality. A structure can be determined to be one-, two- or three-dimensional, depending on the number of directions in space the array extends in. A one-dimensional structure extends in a straight line (along the x axis); a two-dimensional structure extends in a plane (two directions, x and y axes); and a three-dimensional structure extends in all three directions (x, y, and z axes). [3] This is depicted in Figure 1.


The work of Alfred Werner and his contemporaries laid the groundwork for the study of coordination polymers. Many time-honored materials are now recognized as coordination polymers. These include the cyanide complexes Prussian blue and Hofmann clathrates. [4]

Synthesis and propagation

Coordination polymers are often prepared by self-assembly, involving crystallization of a metal salt with a ligand. The mechanisms of crystal engineering and molecular self-assembly are relevant. [2]

Figure 2. Shows planar geometries with 3 coordination and 6 coordination. Planer3and6Coordination.png
Figure 2. Shows planar geometries with 3 coordination and 6 coordination.

Intermolecular forces and bonding

Forces that determine metal-ligand complexes include van der Waals forces, pi-pi interactions, hydrogen bonding, and stabilization of pi bonds by polarized bonds in addition to the coordination bond formed between the metal and the ligand. These intermolecular forces tend to be weak, with a long equilibrium distance (bond length) compared to covalent bonds. The pi-pi interactions between benzene rings, for example, have energy roughly 5–10 kJ/mol and optimum spacing 3.4–3.8 Ångstroms between parallel faces of the rings.


The crystal structure and dimensionality of the coordination polymer is determined by the functionality of the linker and the coordination geometry of the metal center. Dimensionality is generally driven by the metal center which can have the ability to bond to as many as 16 functional sites on linkers; however this is not always the case as dimensionality can be driven by the linker when the linker bonds to more metal centres than the metal centre does linkers. [5] The highest known coordination number of a coordination polymer is 14, [6] though coordination numbers are most often between 2 and 10. [7] Examples of various coordination numbers are shown in planar geometry in Figure 2. In Figure 1 the 1D structure is 2-coordinated, the planar is 4-coordinated, and the 3D is 6-coordinated.

Metal centers

Figure 3. Three coordination polymers of different dimensionality. All three were made using the same ligand (4,5-dihydroxybenzene-1,3-disulfonate (L)), but different metal cations. All of the metals come from Group 2 on the periodic table (alkaline earth metals) and in this case, dimensionality increases with cation size and polarizability. A. [Ca(L)(H2O)4]*H2O B. [Sr(L)(H2O)4]*H2O C.[Ba(L)(H2O)]*H2O In each case, the metal is represented in green. Coordination figure.jpg
Figure 3. Three coordination polymers of different dimensionality. All three were made using the same ligand (4,5-dihydroxybenzene-1,3-disulfonate (L)), but different metal cations. All of the metals come from Group 2 on the periodic table (alkaline earth metals) and in this case, dimensionality increases with cation size and polarizability. A. [Ca(L)(H2O)4]•H2O B. [Sr(L)(H2O)4]•H2O C.[Ba(L)(H2O)]•H2O In each case, the metal is represented in green.

Metal centers, often called nodes or hubs, bond to a specific number of linkers at well defined angles. The number of linkers bound to a node is known as the coordination number, which, along with the angles they are held at, determines the dimensionality of the structure. The coordination number and coordination geometry of a metal center is determined by the nonuniform distribution of electron density around it, and in general the coordination number increases with cation size. Several models, most notably hybridization model and molecular orbital theory, use the Schrödinger equation to predict and explain coordination geometry, however this is difficult in part because of the complex effect of environment on electron density distribution. [9]

Transition metals

Transition metals are commonly used as nodes. Partially filled d orbitals, either in the atom or ion, can hybridize differently depending on environment. This electronic structure causes some of them to exhibit multiple coordination geometries, particularly copper and gold ions which as neutral atoms have full d-orbitals in their outer shells.


Lanthanides are large atoms with coordination numbers varying from 7 to 14. Their coordination environment can be difficult to predict, making them challenging to use as nodes. They offer the possibility of incorporating luminescent components.

Alkali metals and alkaline earth metals

Alkali metals and alkaline earth metals exist as stable cations. Alkali metals readily form cations with stable valence shells, giving them different coordination behavior than lanthanides and transition metals. They are strongly affected by the counterion from the salt used in synthesis, which is difficult to avoid. The coordination polymers shown in Figure 3 are all group two metals. In this case, the dimensionality of these structures increases as the radius of the metal increases down the group (from calcium to strontium to barium).


In most coordination polymers, a ligand (atom or group of atoms) will formally donate a lone pair of electrons to a metal cation and form a coordination complex via a Lewis acid/ base relationship (Lewis acids and bases). Coordination polymers are formed when a ligand has the ability to form multiple coordination bonds and act as a bridge between multiple metal centers. Ligands that can form one coordination bond are referred to as monodentate, but those which form multiple coordination bonds, which could lead to coordination polymers are called polydentate. Polydentate ligands are particularly important because it is through ligands that connect multiple metal centers together that an infinite array is formed. Polydentate ligands can also form multiple bonds to the same metal (which is called chelation). Monodentate ligands are also referred to as terminal because they do not offer a place for the network to continue. Often, coordination polymers will consist of a combination of poly- and monodentate, bridging, chelating, and terminal ligands.

Chemical composition

Almost any type of atom with a lone pair of electrons can be incorporated into a ligand. Ligands that are commonly found in coordination polymers include polypyridines, phenanthrolines, hydroxyquinolines and polycarboxylates. Oxygen and nitrogen atoms are commonly encountered as binding sites, but other atoms, such as sulfur [10] and phosphorus, [11] [12] have been observed.

Ligands and metal cations tend to follow hard soft acid base theory (HSAB) trends. This means that larger, more polarizable soft metals will coordinate more readily with larger more polarizable soft ligands, and small, non-polarizable, hard metals coordinate to small, non-polarizable, hard ligands.

Structural orientation

1,2-Bis(4-pyridyl)ethane is a flexible ligand, which can exist in either gauche or anti conformations. Anti-gauche.svg
1,2-Bis(4-pyridyl)ethane is a flexible ligand, which can exist in either gauche or anti conformations.

Ligands can be flexible or rigid. A rigid ligand is one that has no freedom to rotate around bonds or reorient within a structure. Flexible ligands can bend, rotate around bonds, and reorient themselves. These different conformations create more variety in the structure. There are examples of coordination polymers that include two configurations of the same ligand within one structure, [13] as well as two separate structures where the only difference between them is ligand orientation.

Ligand length

A length of the ligand can be an important factor in determining possibility for formation of a polymeric structure versus non-polymeric (mono- or oligomeric) structures. [14]

Other factors


Besides metal and ligand choice, there are many other factors that affect the structure of the coordination polymer. For example, most metal centers are positively charged ions which exist as salts. The counterion in the salt can affect the overall structure. For example, silver salts such as AgNO3, AgBF4, AgClO4, AgPF6, AgAsF6 and AgSbF6 are all crystallized with the same ligand, the structures vary in terms of the coordination environment of the metal, as well as the dimensionality of the entire coordination polymer. [15]

Crystallization environment

Additionally, variations in the crystallization environment can also change the structure. Changes in pH, [16] exposure to light, or changes in temperature [17] can all change the resulting structure. Influences on the structure based on changes in crystallization environment are determined on a case by case basis.

Guest molecules

The addition and removal of guest molecules can have a large effect on the resulting structure of a coordination polymer. A few examples are (top) change of a linear 1D chain to a zigzag pattern, (middle) staggered 2D sheets to stacked, and (bottom) 3D cubes become more widely spaced. Conformational change.jpg
The addition and removal of guest molecules can have a large effect on the resulting structure of a coordination polymer. A few examples are (top) change of a linear 1D chain to a zigzag pattern, (middle) staggered 2D sheets to stacked, and (bottom) 3D cubes become more widely spaced.

The structure of coordination polymers often incorporates empty space in the form of pores or channels. This empty space is thermodynamically unfavorable. In order to stabilize the structure and prevent collapse, the pores or channels are often occupied by guest molecules. Guest molecules do not form bonds with the surrounding lattice, but sometimes interact via intermolecular forces, such as hydrogen bonding or pi stacking. Most often, the guest molecule will be the solvent that the coordination polymer was crystallized in, but can really be anything (other salts present, atmospheric gases such as oxygen, nitrogen, carbon dioxide, etc.) The presence of the guest molecule can sometimes influence the structure by supporting a pore or channel, where otherwise none would exist.


Coordination polymers are commercialized as dyes. Particularly useful are derivatives of aminophenol. Metal complex dyes using copper or chromium are commonly used for producing dull colors. Tridentate ligand dyes are useful because they are more stable than their bi- or mono-dentate counterparts. [18] [19]

2-aminophenol diaz coup.png 2-aminophenol coord.png

One of the early commercialized coordination polymers are the Hofmann compounds, which have the formula Ni(CN)4Ni(NH3)2. These materials crystallize with small aromatic guests (benzene, certain xylenes), and this selectivity has been exploited commercially for the separation of these hydrocarbons. [20]

Molecular storage

Although not yet practical, porous coordination polymers have potential as molecular sieves in parallel with porous carbon and zeolites. [4] The size and shapes of the pore can be controlled by the linker size and the connecting ligands' length and functional groups. To modify the pore size in order to achieve effective adsorption, nonvolatile guests are intercalated in the porous coordination polymer space to decrease the pore size. Active surface guests can also be used contribute to adsorption. For example, the large-pore MOF-177, 11.8 Å in diameter, can be doped by C60 molecules (6.83 Å in diameter) or polymers with a highly conjugated system in order to increase the surface area for H2 adsorption.

Flexible porous coordination polymers are potentially attractive for molecular storage, since their pore sizes can be altered by physical changes. An example of this might be seen in a polymer that contains gas molecules in its normal state, but upon compression the polymer collapses and releases the stored molecules. Depending on the structure of the polymer, it is possible that the structure be flexible enough that collapsing the pores is reversible and the polymer can be reused to uptake the gas molecules again. [21] The Metal-organic framework page has a detailed section dealing with H2 gas storage.


Luminescent coordination polymers typically feature organic chromophoric ligands, which absorb light and then pass the excitation energy to the metal ion. Coordination polymers are potentially the most versatile luminescent species due to their emission properties being coupled with guest exchange. Luminescent supramolecular architectures have recently attracted much interest because of their potential applications in optoelectronic devices or as fluorescent sensors and probes. Coordination polymers are often more stable (thermo- and solvent-resistant) than purely organic species. For ligands that fluoresce without the presence of the metal linker (not due to LMCT), the intense photoluminescence emission of these materials tend to be magnitudes of order higher than that of the free ligand alone. These materials can be used for designing potential candidates for light emitting diode (LED) devices. The dramatic increase in fluorescence is caused by the increase in rigidity and asymmetry of the ligand when coordinated to the metal center. [22]

Electrical conductivity

Structure of coordination polymers that exhibit conductivity, where M = Fe, Ru, OS; L = octaethylporphyrinato or pthalocyaninato; N belongs to pyrazine or bipyridine. Coord Poly Conductivity.png
Structure of coordination polymers that exhibit conductivity, where M = Fe, Ru, OS; L = octaethylporphyrinato or pthalocyaninato; N belongs to pyrazine or bipyridine.

Coordination polymers can have short inorganic and conjugated organic bridges in their structures, which provide pathways for electrical conduction. example of such coordination polymers are conductive metal organic frameworks. Some one-dimensional coordination polymers built as shown in the figure exhibit conductivities in a range of 1x10−6 to 2x10−1 S/cm. The conductivity is due to the interaction between the metal d-orbital and the pi* level of the bridging ligand. In some cases coordination polymers can have semiconductor behavior. Three-dimensional structures consisting of sheets of silver-containing polymers demonstrate semi-conductivity when the metal centers are aligned, and conduction decreases as the silver atoms go from parallel to perpendicular. [22]


Coordination polymers exhibit many kinds of magnetism. Antiferromagnetism, ferrimagnetism, and ferromagnetism are cooperative phenomena of the magnetic spins within a solid arising from coupling between the spins of the paramagnetic centers. In order to allow efficient magnetic, metal ions should be bridged by small ligands allowing for short metal-metal contacts (such as oxo, cyano, and azido bridges). [22]

Sensor capability

Coordination polymers can also show color changes upon the change of solvent molecules incorporated into the structure. An example of this would be the two Co coordination polymers of the [Re6S8(CN)6]4− cluster that contains water ligands that coordinate to the cobalt atoms. This originally orange solution turns either purple or green with the replacement of water with tetrahydrofuran, and blue upon the addition of diethyl ether. The polymer can thus act as a solvent sensor that physically changes color in the presence of certain solvents. The color changes are attributed to the incoming solvent displacing the water ligands on the cobalt atoms, resulting in a change of their geometry from octahedral to tetrahedral. [22]

Related Research Articles

Coordination complex Molecule or ion containing ligands datively bonded to a central metallic atom

A coordination complex consists of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those that include transition metals, are coordination complexes.

Hydrogen bond Hydrogen Partial intermolecular bonding interaction

A hydrogen bond is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group, and another electronegative atom bearing a lone pair of electrons—the hydrogen bond acceptor (Ac). Such an interacting system is generally denoted Dn–H···Ac, where the solid line denotes a polar covalent bond, and the dotted or dashed line indicates the hydrogen bond. The most frequent donor and acceptor atoms are the second-row elements nitrogen (N), oxygen (O), and fluorine (F).

Ligand Ion or molecule that binds to a central metal atom to form a coordination complex

In coordination chemistry, a ligand is an ion or molecule that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs often through Lewis Bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands".

Organometallic chemistry Study of organic compounds containing metal(s)

Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.

In coordination chemistry, a coordinate covalent bond, also known as a dative bond, dipolar bond, or coordinate bond is a kind of two-center, two-electron covalent bond in which the two electrons derive from the same atom. The bonding of metal ions to ligands involves this kind of interaction. This type of interaction is central to Lewis acid–base theory.

Supramolecular assembly

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. 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.

Octahedral molecular geometry Molecular geometry

In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The octahedron has eight faces, hence the prefix octa. The octahedron is one of the Platonic solids, although octahedral molecules typically have an atom in their centre and no bonds between the ligand atoms. A perfect octahedron belongs to the point group Oh. Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6. The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, [Co(NH3)6]3+, which is not octahedral in the mathematical sense due to the orientation of the N−H bonds, is referred to as octahedral.

The term coordination geometry is used in a number of related fields of chemistry and solid state chemistry/physics.

A non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons, but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. The chemical energy released in the formation of non-covalent interactions is typically on the order of 1–5 kcal/mol (1000–5000 calories per 6.02 × 1023 molecules). Non-covalent interactions can be classified into different categories, such as electrostatic, π-effects, van der Waals forces, and hydrophobic effects.

Uranyl Oxycation of uranium

The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula UO2+
. It has a linear structure with short U–O bonds, indicative of the presence of multiple bonds between uranium and oxygen. Four or more ligands may be bound to the uranyl ion in an equatorial plane around the uranium atom. The uranyl ion forms many complexes, particularly with ligands that have oxygen donor atoms. Complexes of the uranyl ion are important in the extraction of uranium from its ores and in nuclear fuel reprocessing.

Metal–organic framework

Metal–organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. They are a subclass of coordination polymers, with the special feature that they are often porous. The organic ligands included are sometimes referred to as "struts" or "linkers", one example being 1,4-benzenedicarboxylic acid (BDC).

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 electrostaticattraction. 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.

Compounds of zinc are chemical compounds containing the element zinc which is a member of the group 12 of the periodic table. The oxidation state of zinc in most compounds is the group oxidation state of +2. Zinc may be classified as a post-transition main group element with zinc(II). Zinc compounds are noteworthy for their nondescript behavior, they are generally colorless, do not readily engage in redox reactions, and generally adopt symmetrical structures.

Covalent organic frameworks (COFs) are a class of materials 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.

Coordination cages are three-dimensional ordered structures in solution that act as hosts in host–guest chemistry. They are self-assembled in solution from organometallic precursors, and often rely solely on noncovalent interactions rather than covalent bonds. Coordinate bonds are useful in such supramolecular self-assembly because of their versatile geometries. However, there is controversy over calling coordinate bonds noncovalent, as they are typically strong bonds and have covalent character. The combination of a coordination cage and a guest is a type of inclusion compound. Coordination complexes can be used as "nano-laboratories" for synthesis, and to isolate interesting intermediates. The inclusion complexes of a guest inside a coordination cage show intriguing chemistry as well; often, the properties of the cage will change depending on the guest. Coordination complexes are molecular moieties, so they are distinct from clathrates and metal-organic frameworks.

3-Pyridylnicotinamide Chemical compound

The organic compound 3-pyridylnicotinamide (3-pna), also known as N-(pyridin-3-yl)nicotinamide, is a kinked dipodal dipyridine that is synthesized through the reaction of nicotinoyl chloride and 3-aminopyridine. The nitrogen atoms on its pyridine rings, like those of its isomer 4-pyridylnicotinamide, can donate their electron lone pairs to metal cations, allowing it to bridge metal centers and act as a bidentate ligand in coordination polymers. It can be used to synthesize polymers that have potentially useful gas adsorption properties.

Two-dimensional polymer

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.

Some metal-organic frameworks (MOF) display large structural changes as a response to external stimuli, and such modifications of their structure can, in turn, lead to drastic changes in their physical and chemical properties. Such stimuli-responsive MOFs are generally referred to as a flexible metal-organic frameworks. They can also be called dynamic metal-organic framework, stimuli-responsive MOFs, multi-functional MOFs, or soft porous crystals.

Transition metal carboxylate complex

Transition metal carboxylate complexes are coordination complexes with carboxylate (RCO2) ligands. Reflecting the diversity of carboxylic acids, the inventory of metal carboxylates is large. Many are useful commercially, and many have attracted intense scholarly scrutiny. Carboxylates exhibit a variety of coordination modes, most common are κ1- (O-monodentate), κ2 (O,O-bidentate), and bridging.

Carboxylate–based metal–organic frameworks are metal–organic frameworks that are based on organic molecules comprising carboxylate functional groups.


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