Beruflich Dokumente
Kultur Dokumente
[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
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
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
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
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.