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Selective Formation of a Mixed‐Valence State from Linearly Bridged Oligo(aromatic diamines): Drastic Structural Change into a Folded Columnar Stack for Half‐filled Polycations
Author(s) -
Nojo Wataru,
Ishigaki Yusuke,
Takeda Takashi,
Akutagawa Tomoyuki,
Suzuki Takanori
Publication year - 2019
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.201901272
Subject(s) - oligomer , valence (chemistry) , dimer , delocalized electron , stack (abstract data type) , electrical conductor , molecule , materials science , chemical physics , crystallography , chemistry , polymer chemistry , organic chemistry , computer science , composite material , programming language
A method to obtain an organic mixed‐valence state with long‐range delocalization is proposed, which enables the selective generation of half‐filled ( n /2‐charged) polycations from linearly bridged oligomers with n electron‐donating units. When π‐extended phenylenediamine units are connected by meta ‐xylylene‐type spacers, the resulting oligomers adopt non‐folded structures in the neutral state owing to the non‐conjugating and flexible nature of the spacer, whereas the structure shows a drastic change into a one‐dimensional columnar stack upon oxidation to the corresponding half‐filled polycations. Although they are nano‐sized discrete molecules, they can mimic the electronic structure of crystalline organic conductors in a mixed‐valence state. The key for the oligomer design is adoption of the best‐matched spacer that facilitates formation of the singly charged pimer in the dichromophoric system whereas the corresponding doubly charged π‐dimer is disfavored.