Electrochemical Switching in Anthraquinone-Substituted Carbon-Pivot Lariat Ethers and Podands: Chain Length Effects in Geometric and Electronic Cooperativity

Article abstract of DOI:10.1021/ja00284a019

A series of 1-substituted anthraquinones has been synthesized, most often by nucleophilic aromatic substitution on 1-chloroanthraquinone.They have the following structures and were prepared in the indicated yields where E is -CH2CH2- and Aris the 1-substitued anthraquinone: 1, Ar-OCH3, (48percent); 2, Ar-OEOEOCH3 (61percent); 3, Ar-OEOEOEOCH3 (61percent); 4, Ar-OEOEOEOEOCH3 (65percent); 5, Ar-OEOEOEOEOEOCH3 (14percent); 6, Ar-OEOEOEO-Ar (66percent); 7, Ar-O-CH2-15-crown-5 (39percent).Both one- and two-electron time-resolved redox couples (using cyclic voltammetry) are observed for the various systems when 0-1.0 equiv of Li⁺, Na⁺, or K⁺ are added.The electrochemical behavior is complex and is accounted for by a combinations of electronic steric factors.