Coordination chemistry

Part 2: Coordination chemistry in materials

Lecture 8
Dr. Loredana Proteșescu

Assistant Professor
Nanomaterials Chemistry
Zernike Institute for Advanced Materials
www.Protesesculab.com
Lecture 8

1. Recap from lecture 7

2. MOFs with polynuclear building nodes
(secondary building units – SBU)
3. Cation exchange in MOFs

3. Characterisation of MOFs
4. Functions of porous structures and MOFs’ applications

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MOFs and zeolites

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Secondary Building Units (SBUs)

3-c 3-c 4-c 6-c

Zn2(–COO)3 Cu3O(–PZ)3Cl3 Cu2(–COO)4 Zn4O(–COO)6

8-c 12-c 24-c Infinite

Cu4Cl(–COO)8 Cu12(–CDC)12 Cu24(–mBDC)24 [Zn3(–O)3(–COO)3]∞

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 Dinuclear building nodes
Can be linked:
In the axial position In the equatorial position

Example: Cu (R-COO)2 – forms dimers

“paddlewheel”

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Dinuclear building nodes-examples

[Ru2(O2CPh)4]

Chem. Commun., 2005, 865–867 | 865 6

Dinuclear building nodes
Or both axial and equatorial positions

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M3O and M4O building Nodes
Or both axial and equatorial positions

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M3O and M4O building Nodes – examples – exercises in the tutorial

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Nanoscale building Nodes

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Nanoscale building Nodes - example

Crystal Growth & Design, Vol. 7, No. 6, 2007

Communications
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Cation exchange in MOFs

(1) The secondary building units (SBUs) that undergo cation exchange often contain metal sites
that are coordinatively unsaturated, are coordinated by at least one solvent molecule, or are
capable of higher coordination numbers than suggested by the crystal structures of the
respective MOFs.
(2) Metal sites that are coordinatively saturated by the MOF framework/ligands can still undergo
cation exchange if the ligands in the framework form a weak field ligand environment at the SBU.
(3) Although periodic trends of cation exchange are not fully established yet, Cu2+ ions tend to
replace most other second row transition metals, but Pb2+, Mn2+, and Cd2+ exchange faster than
Cu2+.
(4) The structure of the MOF may influence the extent of cation exchange; the primary reason for
this may be the limited distortion allowed by any given lattice during the exchange process.
(5) Applications of cation exchange in MOFs are just emerging, but the technique has already
enabled the formation of previously unknown molecular species, highlighting MOFs as new
platforms for coordination chemistry and small molecule reactivity

(Tutorial Review) Chem. Soc. Rev., 2014, 43,

5456-5467
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Recap octahedra substitution mechanism and apply it for MOFs

Simplified
mechanistic
pathways for cation • flexibility
exchange at MOF • the ability of
SBUs. Green and red metal sites to
spheres represent interact with the
exiting and inserting solvent
metal ions,
respectively. Organic
linkers are shown in
gray and solvent is
depicted in yellow.

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Cation exchange in MOFs - example

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Characterization of MOFs

Crystal Structure
• Single-crystal XRD measurements: internal
lattice of crystalline substances, unit cell
dimensions, bond-lengths, bond-angles, and
details of site-ordering

• Cambridge Structural Database (CSD): the

world’s repository for small-molecule organic
and metal-organic crystal structures.

• 3D structure visualization (free software:

Mercury (CCD); Vesta, TOPOS (topological
representation of MOFs)

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Characterization of MOFs

Chem. Sci.,2021,12,6129–6135 16
microporous (Type I),
nonporous
or macroporous (Types
II, III, and VI), or
mesoporous (Types IV
and V)

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Characterization of MOFs

Thermogravimetric Analysis

• Sample is heated at a constant heating rate

110
• Property Measured: 1.5
100
- Weight (TGA)

- Size (TMA)

DSC / mV mg-1
90 1.0

Weight loss / %
- Heat Flow (DSC) 80
0.5
- Temperature (DTA) 70

- Gas evolved (TPD)

0.0
60

50 -0.5
100 200 300 400 500 600 700
Temperature / 0C

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Stability of Framework Structures

Chemical stability is the ability of a given material to withstand chemical

treatment without any significant change in its structure. This can be evaluated
by subjecting a material to different liquid or gaseous chemicals, followed by
X-ray diffraction analysis to verify that the structure of the material has not been
altered or degraded.
Thermal stability is the ability of a given material to withstand thermal treatment
without any significant change in its structure. This can often be assessed
by thermogravimetric analysis or differential-scanning-calorimetry where, upon
heating the sample, an apparent mass loss or a thermal effect (exothermic or
endothermic) is recorded, indicating decomposition and changes in the structure.
Additionally, X-ray diffraction studies performed on the material after or
during thermal treatment can provide information on whether the structure has
been retained.
Mechanical stability is the ability of a given material to withstand external
forces. Methods to determine the mechanical stability of MOFs are similar
to those used in materials science such as pressurization (compressibility),
nano-indentation (Young’s modulus) or determination of the tensile strength to
name a few.
Architectural stability is the ability of a framework material to retain its structural
integrity in the absence of guest molecules. It can be proven by evacuating
the solvent from the pores of a MOF and subsequent confirmation of its crystal
structure and porosity.
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MOFs – integrated exercise (1)
Porous solids of the formula
M3(BTC)2·12H2O (M = Co, Ni, Zn)
can be synthesised by reacting M(II)
acetate hydrate with 1,3,5-
benzenetricarboxylic acid (H3BTC)
using the hydrothermal method.
The resulting open framework
structure of Co3(BTC)2·12H2O is
constructed from both covalent
interactions and hydrogen bonding
interactions resulting in channels that
are 4×5 Å. These hydrogen bonding
interactions help assemble the
coordination polymer into a porous
framework.
Yaghi, O. M.; Li, H.; Groy, T. L. Construction of Porous Solids from Hydrogen-Bonded Metal Complexes of
1,3,5-Benzenetricarboxylic Acid. J. Am. Chem. Soc. 1996, 118 (38), 9096−9101.
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MOFs – integrated exercise (2)
Q1. Write out the balanced chemical reaction for the
formation of Co3(BTC)2•12H2O.

Q2. The cobalt MOF is reddish in color. What color would

you expect for Zn3(BTC)2•12H2O and Ni3(BTC)2•12H2O?
Explain your answer.

Q3. Explain the transformation from a) to b).

Q4. The thermogram for Co3(BTC)2•12H2O is given below.

What is the temperature range of water loss? Why isn’t all
the water lost/removed at or around 100 °C (the
temperature at which water boils)?

Q5. Describe what would occur with the structure of the

MOF as some of the water molecules are removed and
added.

Q6. A peak in what region of the IR spectrum would

indicate that the ligand coordinated to the metal center?
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Foreseen real-life application of MOFs

Proton and ion (Enantioslective) catalytic

conductivity for fuel cells transformations within the
and battery applications pores

Molecular sensing
Gas adsorption for
alternative fuels
Low temperature
heating and cooling
applications

Separations for clean air

Molecular storage and
separations

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 Commercially available MOFs
Basolite F300 (BASF)

MIL100(Fe)
Q: Suggest two practical applications of this MOFs.
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 Commercially available MOFs

Basolite C300 (BASF)

•Adsorption and storage of gases (carbon

dioxid CO, nitrogen N2, oxygen O2, hydrogen
H2)
•Gas sensing and separation (e.g. CO2)
Formula: C18H6Cu3O12 •Catalysis
Surface area: 1100 – 2200 m2/gr •Ionic and electrical conductivity
•Antifungal
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MOFs as Lewis acid catalysts

R = C6H 5
R1 = CH3

Q: Discuss the catalytic activity results.

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MOFs as Lewis acid catalysts

R = C6H 5

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