Stable Cu+, Ag+ complexes of aza-bridged macrocyclic molecules: Structure and chemical properties

Hiroyuki Takemura, Noriyoshi Kon, Keita Tani, Ko Takehara, Junko Kimoto, Teruo Shinmyozu, Takahiko Inazu

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The cage type compounds 1 and 2 form stable Cu+ or Ag+ complexes, which have been employed for the preparation of cation-free host molecules. A reaction between the potassium complex K+⊂1 and a CuII salt generates a CuI complex. The CuII/CuI redox potential is observed at +0.43 V (vs. SCE) in the cyclic voltammetry, which shows that the Cu+ state is stabilized by its rigid molecular skeleton and spatially fixed coordination sites. A reaction between Ag+ and K+⊂2 yields the dinuclear complex 2Ag+⊂2, which has a short Ag+ ⋯ Ag+ distance (2.78 Å). The halide anions (Cl-, Br-, I-) remove one Ag+ from 2Ag+⊂2 to give Ag+⊂2, but further demetallation does not occur. CV measurements show that these silver complexes are electrochemically stable. Both silver complexes are stable to sunlight. The first preparations of guest-free hosts have been achieved by treating Cu+⊂1 or 2Ag+⊂2 with CN-. Inclusions of neutral guests (NH3, BH3) have been attempted using these guest-free hosts.

Original languageEnglish
Pages (from-to)239-246
Number of pages8
JournalJournal of the Chemical Society - Perkin Transactions 1
Issue number3
DOIs
Publication statusPublished - Feb 7 1997

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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