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 selfassembled 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 selfassembly 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.
We investigated the self-assembly process of a Pd 4 L 8 double-walled square (DWS) from [PdPy* 4 ] 2+ (Py*: 3-chloropyridine used as the leaving ligand on the Pd II center) and an organic ditopic ligand by QASAP (quantitative analysis of selfassembly process). DWS is assembled mainly through three pathways. Within 5 minutes of the self-assembly, all of the substrates, the metal source and the organic ditopic ligand, were completely consumed and converted into primary intermediates. In 2 h, the primary intermediates afforded 30 % of DWS, 200-nm-sized large intermediates, and a relatively stable transient intermediate. This stable intermediate was characterized as a kinetically trapped Pd 3 L 6 double-walled triangle (DWT) by [a]
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.