Rate-determining step in the self-assembly process of supramolecular coordination capsules

Abstract

We present a novel method for investigating the self-assembly process by following the average composition of the fragmentary species.

Self‐Assembly Processes of Pd(II)‐ and Pt(II)‐Linked Discrete Self‐Assemblies Revealed by QASAP

“…However, in some cases we observed almost constant value during the self‐assembly even though the production of the final self‐assembly continued. This special case indicates that the species whose ( n , k ) value is mainly exists as the intermediate and that the conversion of this species is the rate‐determining step in the self‐assembly process (see section 3.1) ,,…”

“…(b) Ligand exchange mechanism on a Pd(II) center. (c) Self‐assembly process of an octahedron‐shaped Pd 6 2 8 capsule . (d) Chemical structure of tritopic ligand 3 .…”

“…Thus, when three p ‐tolyl methyl groups in 2 are replaced with smaller deuterium atoms (tritopic ligand 3 in Figure d), the energy barrier of the intramolecular ligand exchange of Pd 6 3 8 Py would be lower. Indeed, for the self‐assembly of the Pd 6 3 8 capsule, the intramolecular ligand exchange of Pd 6 3 8 Py 2 (Pd 6 3 8 Py 2 Pd 6 3 8 Py+Py) became the rate‐determining step of the self‐assembly …”

Quantitative Analysis of Self‐Assembly Process of a Pd2L4 Cage Consisting of Rigid Ditopic Ligands

“…The main feature of QASAP is that the self‐assembly process is investigated not by the detection of all the intermediates, but by the quantification of all observable species, which include substrates, products, and long‐lived intermediates, from which a time‐dependent concentration of non‐observable species can be obtained by using the principles of mass balance. With QASAP, we have revealed the self‐assembly process of Pd II ‐linked octahedron‐shaped capsules, and Pt II ‐linked hexagonal rings ,. Herein, we report the self‐assembly process of the Pd 2 1 4 cage, formation of which was originally reported by Hooley et al., constructed from rigid ditopic ligand, 1 , in which two 3‐pyridyl groups are connected to a benzene ring through acetylene bonds (Figure ).…”

Supramolecular Chirality in Dynamic Coordination Chemistry

“…complexes, favor a square planar structure suitable for construction of highly ordered chain architectures, including helices and sheets. Among these d 8 metal complexes, Pd(II) complexes often are used for the construction of molecular strands [48], coordination capsules [49], and spherical complexes [50]. Because the Pd(II) center has a hemi-labile coordination bond, dynamic molecular motion and ligand exchange phenomena have been investigated by 1 H NMR spectroscopy as well as other spectroscopic methods.…”