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Energy‐Landscape‐Independent Kinetic Trap of an Incomplete Cage in the Self‐Assembly of a Pd 2 L 4 Cage
Author(s) -
Nakagawa Masanori,
Kai Shumpei,
Kojima Tatsuo,
Hiraoka Shuichi
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801183
Subject(s) - cage , metastability , kinetic energy , chemistry , reactivity (psychology) , trapping , self assembly , ion , energy landscape , activation energy , cage effect , crystallography , chemical physics , photochemistry , physics , organic chemistry , medicine , ecology , biochemistry , alternative medicine , mathematics , pathology , quantum mechanics , combinatorics , biology , photodissociation
A kinetic trap is the metastable species that is transiently or constantly produced during the reaction by trapping in a deep energy well. In most cases, the reactivity of kinetically trapped species is relatively low under the reaction conditions. Herein, we report another type of kinetically trapped species that is an incomplete cage ( IC ) intermediate produced during the self‐assembly of a Pd 2 L 4 cage from ditopic ligand (L) and Pd II ions with a certain lifetime, although IC has a high enough reactivity to be converted into the cage with the reaction of free L, which was confirmed by the reaction of the isolated IC and L under the self‐assembly conditions. IC was kinetically trapped not because IC lies on the bottom of a deep energy well but because the conversion of the intermediates essential for the conversion of IC to the cage preferentially takes place; IC was kinetically trapped independently of the shape of the energy landscape of the self‐assembly.