Inorganic polymers (MOFs, Zeolites, Silicates etc.) What is Metal-Organic Framework? • These are compounds consisting of metal ions or clusters which are coordinated by organic molecules to form one-, two-, or three-dimensional structures • Porous materials • The organic molecules included are sometimes referred to as "struts,“ or linkers What is Metal-Organic Framework? • These are compounds consisting of metal ions or clusters which are coordinated by organic molecules to form one-, two-, or three-dimensional structures • Porous materials • The organic molecules included are sometimes referred to as "struts,“ or linkers How it all got organized
The IUPAC task group on Coordination polymers and metal- organic
frameworks: terminology and nomenclature guidelines
Since 2009, the IUPAC division of Inorganic Chemistry has initiated
above project.
Why? Stockholm Convention
New terminology should also help us COORDINATION to constructively discuss new POLYMER compounds, materials and phenomena without having to proceed through COORDINATION NETWORK endless preambles of definitions.
A final meeting in Stockholm (Sweden) 2012. MOF
Coordination Polymer A coordination compound with repeating coordination entities extending in 1, 2 or 3 dimensions. Comment: • Coordination polymers do not need to be crystalline. • These compounds may in some cases, such as those being composed of carboxylates, be regarded as salts. Ref: Crystengcomm 14, 3001, 2012 • A classical type of single-chain coordination polymer is the (4,4'- bipyridine-N,N)-bridged cobalt(II) compound
Naturforsch.,B:Chem.Sci. 1982, 37, 272.
Coordination Network A coordination compound 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.
Comment: The preferred and most widely understood term will likely be Coordination Polymer, but the IUPAC will endorse also the use of the term Coordination Network although it should be clear that these two terms are not synonymous Coordination Network: Examples
Example of spiro connections forming a Example of a coordination network that is
coordination network also a 3D-coordination polymer Metal-Organic Framework A Metal-Organic Framework, abbreviated to MOF, is a Coordination Network with organic ligands containing potential voids.
Comment: Many systems are dynamic and changes in structure and thus corresponding changes in potential porosity or solvent and guest filled voids may occur depending on temperature, pressure or other external stimuli.
Archetypical MOFs
Crystengcomm 2011, 13, 5813.
Net or network topologies The use of topology to enhance the description of crystal structures of 3D-coordination polymers and MOFs is strongly recommended. Comment: Accurate and careful use of network topologies will make scientific communication more efficient.
IUPAC should not at the present time endorse any other
terms in the area.
The only term that is explicitly discouraged is “hybrid
organic-inorganic materials” Important facts • The size of the interstitial spaces in structures depends largely on the size of the atoms that make up the basic structure • Larger subunits allow for the inclusion of larger molecules i.e., solvent molecules • Many structures release these solvent molecules but tend to collapse without them • Recently, metal-organic frameworks (MOF) have garnered a lot of attention because of their unique properties. ✓ They consist of a metal ion and an organic ligand that links the metal ions together into larger arrays. ✓ Many dicarboxylic acids (oxalic, malonic, succinic, glutaric, terephthalic), tricarboxylic acids (citric, trimesic) or azoles (1,2,3-triazole, pyrrodiazole) are used as linker. MOF-5: geometry a) The view along fourfold axis of the metal–organic framework structure in 1:4 DMF-H2O. One {Zn2(1,4-bdc)2} 2D Layer is colored orange to emphasize the alternation of stacking layer. H-atoms and guest molecules are omitted. b) Space-filling representation of evacuated framework, which emphasizes the open square channels; view along fourfold axis. c) Side view of evacuated framework, showing the windows interconnecting the channels. d) Space-filing representation of the metal–organic framework structure in C6H6, showing rhombic- grid motif of {Zn2(1,4-bdc)2} layers. The guest molecules and DABCO hydrogens are not shown Zn green; N blue; O red; C grey; H white. Angew Chem, 116, 2004, 5143 MOF-5: Facts • MOF-5 (Zn4O(1,4- benzenedicarboxylate)3, 0.13-0.20 g/cm3) consists of tetrahedral [Zn4O]6+ units that are linked together with 1,4- benzene-dicarboxylate units. The opening in the structure is 9.3-13.8 Å depending on the orientation of the ring • MOF-5 can store a significant amount of hydrogen at low temperature [77 K: 7.1 wt % (40 bar), 10 wt % (100 bar)] • While the hydrogen storage capacity in decent at 77 K (66 g/L), its ability to store hydrogen at room temperature is significantly lower (9.1 g/L), which limits its use as hydrogen storage medium More MOFs
• MOF-177 (Zn4O(1,3,5-benzenetribenzoate)2) also consists
of tetrahedral [Zn4O]6+ units are linked by large, triangular tricarboxylate ligands.
• Its hydrogen storage capacity
is similar to the one of MOF-5 [77 K: 7.1 wt % (40 bar), 11.4 wt % (78 bar)] • MOF-200 and MOF-210 display a little bit higher uptake of hydrogen at low temperature and are able to deliver 3 % at 100 bar at room temperature. More MOFs • MIL-53 ([Al(OH)3] (1,4-benzenedicarboxylate) (1,4-benzenedicarboxylic acid)0.7, 0.4 g/cm3) consists linear chains of [AlO4(OH)2] octahedra that are linked together with 1,4-benzene- dicarboxylate units. • Like many other MOFs, it is obtained by the reaction of the metal nitrate with the dicarboxylic acid under hydrothermal conditions (synthesis of single crystals that depends on the solubility of minerals in hot water under high pressure, important in geochemistry)
• Recently, the iron, chromium and scandium analog of MIL-53
have been prepared as well. • MIL-101 (Cr3O(F/OH)(H2O)2(1,4-benzenedicarboxylate)3) and MIL-100 (Fe) (Fe3OF(H2O)2 ((1,3,5-benzenetribenzoate)2) are variations of MIL-53 using iron or chromium as metal center and fluoride or hydroxide ligands in addition to the organic linkers. More MOFs • HKUST-1 (Cu3(1,3,5- benzenetribenzoate)2, 0.35 g/cm3, Basolite C300) is a copper-based MOF whose thin films could be used in applications including photovoltaics, sensors and electronic materials
• ZIF-8 (Zn(C4H5N2)2, 0.35
g/cm3, Basolite Z1200) is a zinc-2-methylimidazoline compound. Solvatochromism / Vapochromism • One of the simplest, and arguably most powerful, means of transducing a sensing signal is a visible change in a material’s color • Solvatochromism refers to a large shift in the absorption spectrum of a material in response to a change in the identity of the solvent. Often the shifts correlate with empirical measures of solvent polarity, implying that the electronic transition responsible for the coloration entails charge transfer, that is, a change in dipole moment upon excitation from the ground to the excited electronic state of the chromophoric component of the material • If the excited state features a larger dipole moment than the ground state, it is preferentially stabilized by polar solvents, and bathochromic shifts (red shifts) are observed with increasing solvent polarity. • Conversely, if the ground state has the larger dipole moment, hypsochromic shifts (blue shifts) occur with increasing solvent polarity. • For a chromophore embedded in a MOF (for example, as a linker), sorption of vapor is the equivalent of solvating a molecular absorber, and vapochromic trends should match solvatochromic ones. Solvatochromism / Vapochromism
3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine
Visible spectra and photograph of MOF
crystals containing solvents (condensed vapors). A negative vapochromic effect is observed for both hydroxylic and nonhydroxylic vapors (solvents). J. Am. Chem. Soc. 2011, 133, 4172 Sensing of Chloride
(A)Cartoon of MOF-coated capillary for sensing chloride gas. (B) Photo of capillary as made (a), after 10 s (b), and after 30 s (c) exposure to 100 mM chloride-containing vapor or gas. (C) Photo of MOF pellet (a) as prepared, (b) after exposure to phosgene gas, and (c) after rinsing with 100mM HBr to regenerate original structure.
Chem.-Eur. J. 2011, 17, 2823
Luminescence-Based Sensing BTC =
Molecular-packing diagram viewed along the c-axis,
showing open metal sites in 1-D channels created in 3-D supramolecular metal-organic framework. Zn3(BTC)2 12H2O
Two research groups have shown how molecular sieving can be used for size selective sensing in luminescent Zn3btc2 (btc = benzenetricarboxylate).
✓ Following exposure to amines of different sizes, a decrease in the
fluorescence was observed for amines that were small enough to easily diffuse into the MOF pores, including ethylamine, dimethylamine, and propylamine.
✓ In contrast, aniline and butylamine showed no quenching, presumably due to
size exclusion. Applications: MOF as Gas storage Chemical sensors Separation Heterogeneous catalysis Simple Lab Projects • Synthesize a-magnesium formate, which also displays MOF–type properties as well, in solvothermal fashion • Since the synthesis of a-Mg3(O2CH)6 is carried out in N,N- dimethylformamide, the solvent will be included into the porous structure
• Upon heating under reduced pressure, the guest can be removed without disrupting the framework as the crystal structure of the two compounds demonstrates. • Other molecules (i.e., THF, Et2O, MeOH, EtOH, C6H6, C7H8, C6H12, etc.) may or may not be used to fill the voids of the guest-free structure depending on their size • Characterization by FT-IR (ATR), 1H-NMR and 13C-NMR spectrum(D2O) Thermogravimetric Analysis (TGA) • What do you expect in a TGA of MOF-5?? • The loss of solvent starts at 130 oC leading to the solvent free compound, which has a mass of 82.4 % of the original compound • At 400 oC, a-magnesium formate thermally decomposes to form MgO (29.0 %) Zeolites and Silicates Catenation Definition: The property of an element to form extensive stable bonding of the atoms of the same element in series (open and closed ended). If open – chains, if closed – rings (or cages) Features 1. Not common with all elements in periodic table – typically observed with main group elements such 2. Stabilization of the catenation products are mostly based on the energy aspects of formation vs. decomposition, reactivity (activation energy), stereo-electronic conditions and electronegativity etc. 3. This is prime for C showing the wide variety of different class of compounds. Other prominent elements of interest showing catenation are Si, S, B Si-Catenation Other than C, Si is the next most important element showing such behavior and also from the application perspective Features of catenation chains 1. Silanes: In comparison to alkanes, the Si-Si bonds are weaker than the C-C, but that is not responsible for the stability differences. Contrarily, the easy decomposition pathway available for silanes than for alkanes, explains it. The difference in activation energy of the two reactions shows the relative inertness of alkanes than silanes CnH2n+2 + (3n+1)/2 O2 → nCO2 + (n+1)H2O SinH2n+2 + (3n+1)/2 O2 → nSiO2 + (n+1)H2O 2. Difficult synthesis and separation methodology for silanes. Isolated upto n=8 3. Polysilanes are well-known with two R’s replacing 2H’s. 4. Fluorinated and Bulky substituents can stabilize silanes better than alkanes, e.g. Si2Br6 boils at 265 °C while C2Br6 breaks into C2Br4 and Br2 at 200 C Catenation in other elements • Germanes are similar to that of the silanes • Distannane is feasible but very unstable • PbH4 is also similarly unstable but Pb(PbPh3)4 is known to be isolated • Other non-metals such as N, P and S forns catenation chains • Hydrazoic acid HN3, hydrazine NH2-NH2 are stable at RT are most prominent N-catenate, higher analogs till N8 are known but explosive • 2-tetrazene, H2N-N=N-NH2 can be stabilized better with substituents • Sulfanes, HSnH are also feasible upto n=8, • Phosphine, PH3 are also fairly extensive with diphosphine (P2H6), triphosphine (H2PPHPH2), and tetraphosphine (H2PPHPHPH2) • O-chains are rare except for 3 atoms as in Ozone, O3, O3-. Another good example is the F3COOOCF3, bis(perfluoroalkyl)trioxide Hetero-Catenation: Silicates • Secondary building units (SBU) for zeolites Hetero-Catenation: Silicates • Si forms numerous hetero-catenates with different elements • Most important are silicates which are parts of all minerals obtained in Earth’s crust, simplest being SiO44- (orthosilicate, not that abundant). Other important minerals being used globally. • Synthetic materials : Zeolites, AlPOs, mesoporous matrices and macroporous ones • Natural zeolites etc. have been used for water purification or water removal from solvents etc. • Size of pores/ porous structures are important in classification • Designed structures based on requirements Zeolites
• Chemically and thermally stable • Industry: Excellent catalysts, molecular sieves, ion- exchangers, water softeners •170 different types, about 17 of them commercial interest Zeolites
+ + Na+ =
• Consist of interconnected SiO2 and AlO2 tetrahedra &
Cations • Tetrahedra form 3D frameworks with linked channels down to molecular level • High porosity, pores fixed down to nm sizes -> gas sensing • Exceptionally high specific-surface-area Zeolite Building blocks
SiO2 tetrahedra
Tetrahedra connected at corners
Each Oxygen is shared by 2 tetrahedra. All corners are connected 4 × ½ = 2 O atoms Si Schematically, oxygen are shown as O Si O Si straight lines (bonds) and Si at the corners O O All corners are connected → 4 lines Si Si from each Si Zeolite - Silicalite (MFI)
1-D channels Si
Si O
All bonds are homopolar →
no polarity in the crystal → Extremely hydrophobic Zeolite - Silicalite (MFI)
Simplified planar view
(SiO2) Zeolite LTA, Si/Al = 1 +
+ +
+ + + Na
Na+ [(SiO2) (AlO2)- ]. zH2O
Zeolite LTA, Si/Al = 1
Cations cause polarity → attract polar molecules (water, CO2)
Zeolite FAU, Si/Al ≠1
+ +
(Na+, Ca++)
Xm+y/m [(SiO2)x (AlO2)-y ]. zH2O
Molecular sieves Important facts • Natural molecular sieves have been used for ion exchange or water removal from solvents etc. • Synthetic molecular sieve materials : Zeolites, AlPOs, mesoporous matrices and macroporous clays etc. • All zeolites are molecular sieves but all molecular sieves are not zeolites
• Size of pores/ porous structures are important in classification:
pore size < 20 Å = Microporous 20 Å < pore size < 200 Å = Mesoporous pore size > 200 Å = Macroporous/ open framework Structurally, the zeolite is a crystalline aluminosilicate with a framework based on an extensive three-dimensional network of oxygen ions. Either a Si+4 or an Al+3 ion is situated within the tetrahedron. The AlO2- tetrahedra in the structure determine the framework charge. This is balanced by cations that occupy nonframework positions. Zeolite structures Faujasite (Zeolite Y shown as example) Applications of zeolites
