TY - JOUR
T1 - Stoichiometry alone can steer supramolecular systems on complex free energy surfaces with high selectivity
AU - Komáromy, Dávid
AU - Tiemersma-Wegman, Theodora
AU - Kemmink, Johan
AU - Portale, Giuseppe
AU - Adamski, Paul R.
AU - Blokhuis, Alex
AU - Aalbers, Friso S.
AU - Marić, Ivana
AU - Santiago, Guillermo Monreal
AU - Ottelé, Jim
AU - Sood, Ankush
AU - Saggiomo, Vittorio
AU - Liu, Bin
AU - van der Meulen, Pieter
AU - Otto, Sijbren
N1 - Funding Information:
We are grateful to ERC (AdG ToDL 741774), the EU (Marie-Sklodowska-Curie grant 847675), the NWO, and the Dutch Ministry of Education, Culture, and Science (Gravitation program 024.001.035) for financial support. Bartosz Matysiak, Dr. Ga?l Schaeffer, and Dr. Charalampos G. Pappas are gratefully acknowledged for fruitful discussions. D.K. and S.O. conceived the project. D.K. S.O. I.M. J.K. and G.P. designed the experiments. D.K. prepared the libraries, performed UPLC, LC-MS, and spectroscopy analyses. T.T.-W. performed Orbitrap ESI-MS analyses. J.K. and P.v.d.M. performed NMR measurements on 1 and 1143. D.K. J.K. and B.L. analyzed and interpreted NMR data. D.K. and B.L. isolated 1143. V.S. synthesized building block 6. P.R.A. performed control experiments and thermal annealing experiments. J.O. performed negative staining TEM measurements, G.M.S. performed cryo-TEM measurements, I.M. performed AFM measurements, F.S.A. performed SDS-PAGE analysis, G.P. and A.S. performed SAXS analysis, and A.S. performed UV-VIS analysis. A.B. interpreted thermodynamic data. D.K. and S.O. wrote the manuscript, with input from A.B. J.K. and G.P. The authors declare no competing interests.
Funding Information:
We are grateful to ERC (AdG ToDL 741774 ), the EU (Marie-Sklodowska-Curie grant 847675), the NWO , and the Dutch Ministry of Education, Culture, and Science (Gravitation program 024.001.035 ) for financial support. Bartosz Matysiak, Dr. Gaël Schaeffer, and Dr. Charalampos G. Pappas are gratefully acknowledged for fruitful discussions.
Publisher Copyright:
© 2021 Elsevier Inc.
PY - 2021/7/8
Y1 - 2021/7/8
N2 - Self-assembly enables access to complex molecular architectures but is traditionally confined to structures that represent global minima on the Gibbs energy landscape. We now report that it is possible to access structures other than those with the lowest individual Gibbs energy, while remaining under thermodynamic control. We prepared dynamic combinatorial libraries from two building blocks possessing complementary binding motifs. Depending on the building block stoichiometry, one of three competing self-assembling macrocycles can be formed with remarkable selectivity. By mixing the same two building blocks, we could access a self-replicating octamer, self-assembling into fibers; a hexamer with a precise 4:2 building block stoichiometry, assembling into hexagonally packed fiber bundles; and a tetramer with 1:3 building block ratio affording a [c3]daisy chain pseudorotaxane. Thus, systems chemistry approaches can enhance the versatility of self-assembly by allowing to navigate complex Gibbs energy landscapes to access structures beyond those that are individually the most stable.
AB - Self-assembly enables access to complex molecular architectures but is traditionally confined to structures that represent global minima on the Gibbs energy landscape. We now report that it is possible to access structures other than those with the lowest individual Gibbs energy, while remaining under thermodynamic control. We prepared dynamic combinatorial libraries from two building blocks possessing complementary binding motifs. Depending on the building block stoichiometry, one of three competing self-assembling macrocycles can be formed with remarkable selectivity. By mixing the same two building blocks, we could access a self-replicating octamer, self-assembling into fibers; a hexamer with a precise 4:2 building block stoichiometry, assembling into hexagonally packed fiber bundles; and a tetramer with 1:3 building block ratio affording a [c3]daisy chain pseudorotaxane. Thus, systems chemistry approaches can enhance the versatility of self-assembly by allowing to navigate complex Gibbs energy landscapes to access structures beyond those that are individually the most stable.
KW - dynamic combinatorial chemistry
KW - self-assembly
KW - self-sorting
KW - supramolecular chemistry
KW - systems chemistry
UR - https://www.scopus.com/pages/publications/85109023303
U2 - 10.1016/j.chempr.2021.05.020
DO - 10.1016/j.chempr.2021.05.020
M3 - Article
AN - SCOPUS:85109023303
SN - 2451-9308
VL - 7
SP - 1933
EP - 1951
JO - Chem
JF - Chem
IS - 7
ER -