Publication

Benzidine/Quinoidal-Benzidine Linked, Superbenzene Based π-Conjugated Chiral Macrocycles and Cyclophanes

LI GUANGWU
Matsuno, T.
Han, Y.
PHAN VAN HOA
Wu, S
Jiang, Q.
Zou, Y.
Isobe, H.
Wu Jishan
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Abstract
Synthesis of fully conjugated cyclophanes containing large-size polycyclic aromatics is challenging. Now, three benzidine-linked, hexa-peri-hexabenzocoronene (superbenzene)-based ortho-, para-, and meta-cyclophanes are synthesized through intermolecular Yamamoto coupling reaction of structurally pre-organized precursors. Subsequent oxidative dehydrogenation gave the corresponding quinoidal benzidine-linked cyclophanes. Their geometries were confirmed by X-ray crystallographic analysis and their electronic properties were investigated by electronic absorption, cyclic voltammetry, and DFT calculations. The quinoidal benzidine-linked cyclophanes show thermally populated paramagnetic activity with a relatively large singlet-triplet energy gap. Two enantiomers for the ortho-cyclophanes (1-NH and 1-N) were isolated and their chiral figure-of-eight macrocyclic structures were identified. The cage-like cyclophanes 2-NH and 3-NH with concave surface can selectively encapsulate fullerene C70.
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Source Title
Angewandte Chemie - International Edition
Publisher
Wiley-VCH
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