Cation Exchange at MOF

[1] C. K. Brozek and M. Dinca (2014): Cation Exchange at secondary building units of metal-organic
framework, Chem. Soc. Rev., 2014, 43, 5456-5467

[2] Transmetalation: routes to metal exchange within metal-organic framework, J. Mater. Chem. A,
2013, 1, 5453-5468

1. Mutual replacement of ions in magmatic materials:

a) Ion exchange can occur if they possess similar charge and radii
b) Ions with greater charge or smaller radii are incorporated to a great degree because they form
stronger, more ionic bonds
c) Ions with similar electronegativity replace each other, with ions with lower value will be exchanged
more because it will form bonds with greater ionic character

2. Observations
a) Exchangeable metal ions in a secondary building unit (SBU) are often capable of higher coordination
numbers than those observed in the X-ray crystal structure
Example: M-MOF-5 (replacement of Zn2+ with other metal ions); ZIF-series (replacement of Zn2+ with
Mn2+ ions); MFU-4l (replacement of Zn2+ with Co2+ ions)
b) Not all structures can be desolvated but the metal sites in many other SBUs typically feature bound
solvent molecules, such as Zn-HKUST-1 (Zn3BTC2(H2O)3), P-MOF-2 (Zn24TDCPEB8(H2O)12), PCN-921
(Zn4(ETTB).4DMF.xSolvent; [Zn7(PPBOTCDITC)3(H2O)7]nZn5((PPBOTCDITC)3)(H2O)5]n.xSolvent, and
other examples)
c) SBU with metal sites that are octahedrally coordinated by the framework ligands and have no
terminal solvent species typically do not undergo cation exchange. However, it might still be possible
if their weak field ligands can dissociate readily
d) M-MOF-74 series are not possible to undergo ion-exchange because any distortion to the [–M2+–
O2–M2+–]∞ would require a large activation energy imposed by the lattice
e) Metastasis with salts of monovalent cations (Li+ or Cu+) resulted in either very little exchange or
almost negligible substitution due to the confinement of singly charged cations resulting in possible
strong charge repulsion

3. Preferential of metal ions to undergo ion-exchange

a) Ligand exchange by Cu2+: In general trend, it is usually replaced at the greatest extent and least
reversible. Besides, Zn2+-type MOF in most cases can be exchanged with Cu2+ due to its ionic diameter
and versatility (ability to adopt unusual coordination geometries)
b) Outside the first transition series, Pb2+ and Cd2+ tend to exchange preferentially into SBUs over Cu2+
and other transition metals
c) The dominance of Cu2+ among these examples and the preference of Cd2+ and Pb2+ over Cu2+ might
be explained by differences in electronegativity. Pb2+ has the lowest electronegativity among the
cations that undergo exchange, followed by Mn2+ and Cd2+. Cu2+ on the other hand has highest
electronegativity. Besides, it is claimed that labile ionic bonds can be made possible by allowing Pb2+,
Mn2+ and Cd2+ ions to perform cation exchange faster
d) Preferential coordination geometry: For metals that are bind via tetrahedral or octahedral
arrangement, it is evident that tetrahedral arrangement will be replaced during ion exchanged,
whereas octahedral centres remain inert to transmetalation
e) Robustness and stability of parent framework: Robustness of the framework does not necessary
preclude a MOF from undergoing transmetallation (example: Zr4+ centres in UiO-66 and Al3+ centres
in MIL-53, which possess strong bond between linkers and metal centres due to its high coordination
number). However, this very robustness can possibly limit the extent of metal exchange and may
prevent the acquisition of homometallic framework.

4. Possible flaws/issues in ion-exchange

a) The resulting crystal may crack if Cu2+ is used in the replacement, as shown in some examples of
MOFs
b) Collapse pores may also present, which leads to reduction in surface area
c) The framework may limit the extent of ion exchange. Longer linkers endow the lattice with greater
flexibility even if the structure is the same
d) Larger particles might better accommodate distortions and defects introduced by the exchange
process than a small one

5. Effect of solvent on ion-exchange ability

a) Most SBU feature coordinatively unsaturated metal sites or solvent ligands, it is significant that all
exchanges involve coordinating solvents. In most cases, methanol, DMF or H2O are used (strongly
donating ligands with relatively high ligand field strengths).
b) Transmetallation is very sensitive to solvent, for example metal exchange showed a faster rate in
methanol than in acetone
c) Attempt on synthesis procedures with multiple solvents and plot the extent of exchange versus
relevant solvent parameters

6. Applications:
It is usually useful if the MOFs produced cannot be achieved via conventional synthetic routes
a) Gas storage: Installation of cations with open coordination sites and open shell electronic structures
enhances the adsorption interaction between the SBU and guest molecule to increase overall gas
uptake
b) Catalysis: There is still not significant to demonstrate how the new SBUs compare with the
heterogeneous catalysts for a given transformation

7. Possible observed differences in cation exchange process:

a) Variation in both size and coordination properties of the parent metal ion and the ion being
exchanged into the framework (kinetic barriers, diffusion problem due to limited pore sizes, steric
hindrance caused by organic struts and confinement in unusual coordination geometries)
b) Metal-ligand binding strength or coordinative flexibility of the framework ligand
c) If the attempted concentrations of exchange salt solution did not exceed a 1:1 stoichiometric ratio
of metal ion to polymer, it can lead to an equilibrium mixture when comparable binding constants are
present
d) Reaction time to effect complete exchange is also a matter to be considered.

8. Partial Metal Exchange

a) Partial metal exchange is usually much more evident than complete metal exchange, as explained
in 7(a)
b) Metal sorption took place exclusively when the polymer was ground to fine powder, whereas only
metal exchange took place in single crystalline sample
c) Lower concentration of metal ions favoured metal sorption whereas at higher concentrations
predominantly metal exchange took place (It has to be substantially exceed the amount of polymer-
bound metal nodes being soaked in the solution in order to shift the equilibrium towards metal
exchange)

9. Core Shell Metal Exchange

a) It provides a route to structures otherwise unattainable via epitaxial growth of one crystal around
the seed
b) Zn2+ (e.g. in Zn-HKUST-1, PMOF-2, M6(BTB)4(bpy)3) experiences transmetallation with other
solutions rather than epitaxial growth, thus core shell growth technique could be used in future for
application including catalysis with multiple metals or selective linker exchange controlled by linker-
metal bond strength
c) In paddle wheel systems, the trend in stability appears to rank from most to least stable Cu > Ni >
Co > Zn. The metals closer to the surface are exchanged at a more rapid rate due to increased flexibility
at the crystal surface based on similar TGA behaviour between ground and large particle samples of
core-shell structures. Besides, another possible reason is that outside of crystal exchange metals is
faster simply due to the time it takes for the metal solution to diffuse to the core of MOF crystals.

10. Complete Metal Exchange

a) Framework containing nodes with geometries adaptable for other metal cations such as
mononuclear octahedral or binuclear paddlewheel motifs appears to be attractive because they are
common in solid-state structures of many coordination compounds
b) Examples: Zn- and Cu- based paddlewheel system

11. Metal Exchange on Struts (Linkers): In gas adsorption studies, the MOF struts can more easily
interact with sorbed gases than the metal nodes due to reduced steric hindrance

12. Outlook:
a) If MOF appears active for cation exchange, then the substitution should be attempted for a variety
of metal species and solvent to tease out trends
b) The rate and extent of exchange under these different conditions could be compared against
various chemical properties of the metal ions and solvents to find parameters that are most relevant
to the mechanism
c) Metals are most easily exchanged for other metals with similar ionic radii and coordination modes,
for example Cu2+ readily replaces Zn2+ and Cd2+, and the exchange appear to the irreversible
d) Concentration of the exchange solution can determine whether new metal ions are adsorbed
through post-synthesis exchange
e) The rate of exchange can be affected by the affinity of the metal for the linker binding group,
framework flexibility and pore diameter

[3] Xiaokai Song, Seok Jeong, Dongwook Kim, Myoung Soo Lah, “Transmetalation in two metal-organic
frameworks with different framework flexibilities: Kinetics and core-shell heterostructures”,
CrystEngComm, 2012, 14, 5753-5756

1. Comparison of the data using transmetallation of Zn-HKUST-1 and Cu-HKUST-1 (ion-exchanged,

incomplete); Zn-PMOF-2 and Cu-PMOF-2 (ion-exchanged, complete)

BET Surface Area

 MOF Formula BET surface area Langmuir Pore volume
2 3
(m /g) surface area (cm /g)
(m2/g)
Zn-HKUST-1 [Zn3(BTC)2(H2O)3] No data can be obtained due to the structure is not
stable
Cu0.46Zn0.54- [(Cu3)0.46(BTC)2(Zn3)0.54
770 890 0.32
HKUST-1 (H2O)3]
Cu0.56Zn0.44- [(Cu3)0.56(BTC)2(Zn3)0.44 980 1120 0.40
HKUST-1 (H2O)3]
Cu-HKUST-1 [Cu3(BTC)2(H2O)3] 1460 1710 0.61

BET Adsorption Isotherm (N2 at 77 K)

Important Observation(s):
1. Zn3(BTC)2 cannot possess complete ion exchange (to Cu), and the reverse transmetallation from
Cu3(BTC)2 to Zn3(BTC)2 is not possible, which demonstrate that Cu3(BTC)2 is thermodynamically more
stable than Zn3(BTC)2.
2. Zn-PMOF-2 can possess complete ion exchange (to Cu), and the reverse transmetallation from Cu-
PMOF-2 to Zn-PMOF-2 is not possible, due to the same reasoning as above
3. Choice of soaking solvent is important. Methanol shows much more meaningful transmetallation
as compared to DMF (possibly due to slow exchange kinetics). Besides, using DMF at an elevated
temperature (70 oC) was complicated because of the formation of blue powder as side product during
the transmetallation process.