TY - JOUR
T1 - Bifurcation of self-assembly pathways to sheet or cage controlled by kinetic template effect
AU - Foianesi-Takeshige, Leonardo Hayato
AU - Takahashi, Satoshi
AU - Tateishi, Tomoki
AU - Sekine, Ryosuke
AU - Okazawa, Atsushi
AU - Zhu, Wenchao
AU - Kojima, Tatsuo
AU - Harano, Koji
AU - Nakamura, Eiichi
AU - Sato, Hirofumi
AU - Hiraoka, Shuichi
N1 - Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers 19H02731, 19K22196, 19K15531, 19H05459, and 19H04563 and The Asahi Glass Foundation.
Publisher Copyright:
© 2019, The Author(s).
PY - 2019/12/1
Y1 - 2019/12/1
N2 - The template effect is a key feature to control the arrangement of building blocks in assemblies, but its kinetic nature remains elusive compared to the thermodynamic aspects, with the exception of very simple reactions. Here we report a kinetic template effect in a self-assembled cage composed of flexible ditopic ligands and Pd(II) ions. Without template anion, a micrometer-sized sheet is kinetically trapped (off-pathway), which is converted into the thermodynamically most stable cage by the template anion. When the template anion is present from the start, the cage is selectively produced by the preferential cyclization of a dinuclear intermediate (on-pathway). Quantitative and numerical analyses of the self-assembly of the cage on the on-pathway revealed that the accelerating effect of the template is stronger for the early stage reactions of the self-assembly than for the final cage formation step itself, indicating the kinetic template effect.
AB - The template effect is a key feature to control the arrangement of building blocks in assemblies, but its kinetic nature remains elusive compared to the thermodynamic aspects, with the exception of very simple reactions. Here we report a kinetic template effect in a self-assembled cage composed of flexible ditopic ligands and Pd(II) ions. Without template anion, a micrometer-sized sheet is kinetically trapped (off-pathway), which is converted into the thermodynamically most stable cage by the template anion. When the template anion is present from the start, the cage is selectively produced by the preferential cyclization of a dinuclear intermediate (on-pathway). Quantitative and numerical analyses of the self-assembly of the cage on the on-pathway revealed that the accelerating effect of the template is stronger for the early stage reactions of the self-assembly than for the final cage formation step itself, indicating the kinetic template effect.
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U2 - 10.1038/s42004-019-0232-2
DO - 10.1038/s42004-019-0232-2
M3 - Article
AN - SCOPUS:85075164836
SN - 2399-3669
VL - 2
JO - Communications Chemistry
JF - Communications Chemistry
IS - 1
M1 - 128
ER -