Abstract

The self-assembly process of a Pd12 L24 sphere was revealed by a quantitative approach (quantitative analysis of self-assembly process: QASAP) quantifying all the substrates, the products, and the observable intermediates, indicating that the Pd12 L24 sphere is produced through several pathways. Firstly, Pdn L2n (n=6, 8, and 9), which are perfectly closed structures smaller than the Pd12 L24 sphere, and a mixture of intermediates not observed by NMR (Int) were produced. Next, the sphere was assembled from intra-/intermolecular reaction of a certain class of Int (path A) and from the coordination of free pyridyl groups in Int to the PdII center of Pdn L2n (n=6, 8, and 9) (path B). While capping the free pyridyl groups in Int with PdII ions perfectly inhibited the sphere formation, the addition of free L to Int accelerated the formation of the sphere.

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