Self-Assembly of Bile Acid Derivatives into Metallosupramolecur Cages
Subhasis Chattopadhyaya,b,c
, Radek Mareka,c
, Ondřej Jurčeka,b,c
*
a
Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, 62500 Brno, Czech Republic;
subhasischattopadyay101@gmail.com
b
Department of Natural Drugs, Faculty of Pharmacy, Masaryk University, 61200 Brno, Czech Republic
c
CEITEC - Central European Institute of Technology, Masaryk University, Kamenice 5, 62500 Brno, Czech
Republic
Natural chiral hydrophobic cavity/pocket containing structures (e.g., metalloenzymes, proteins)
are important for many biological functions (e.g., transport, recognition, catalysis). To mimic
these natural systems and mechanisms, development of such supramolecular systems (e.g.,
cages, macrocycles) from chiral natural molecules is required.
Coordination-driven self-assembly is a well-established method to build hollow
metallosupramolecular (MSM) structures. However, majority of self-assemblies are made of
symmetric, achiral ligands (L) and Pd2+
. Recently in our group, first bile acid (BA)-based
(ursodeoxycholic acid, UDCA) MSM macrocycles Pd3L6 (Figure 1a) were introduced1
and
studied.2
Beside this, there is only one report about BA-based Pd2L4 MSM cages.3
We further
expanded on the family of BAs by synthesizing chenodeoxycholic acid-based ditopic pyridyl
ligand, forms a mixture of PdnL2n species ranging from Pd2L4 to a large Pd6L12.
Figure 1. UDCA-based metallosupramolecular a) macrocycle and b) cage.
Thus far, only BA-based ditopic pyridyl ligands were used to prepare MSM systems. Therefore,
our latest study presents UDCA-based tritopic pyridyl ligand and its self-assembly with Pd2+
,
which results in Pd6L8 or first-ever giant Pd12L16 (Figure 1b) MSM cage depending on solvent
and metal-ligand ratio.
These studies provide better understanding of unsymmetric natural molecule-based ligands
self-assembly, effect of their flexibility, topicity, and bend angle in design and construction of
chiral cavity containing MSM architectures.
1. Jurček, O.; Bonakdarzadeh, P.; Kalenius, E.; Linnanto, J. M.; Groessl, M.; Knochenmuss, R.;
Ihalainen, J. A.; Rissanen, K. Angew. Chem. Int. Ed. 2015, 54 (51), 15462-15467.
2. Jurček, O.; Nonappa, Kalenius, E.; Jurček, P.; Linnanto, J. M.; Puttreddy, R.; Valkenier, H.;
Houbenov, N.; Babiak, M.; Peterek, M.; Davis, A. P.; Marek, R.; Rissanen, K. Cell Rep. Phys.
Sci. 2021, 2 (1), 100303-100323.
3. Sen, S. K.; Natarajan, R. Inorg. Chem. 2019, 58 (11), 7180-7188.