The introduction of a higher arene unit as a structural motif is unprecedented in calixphyrin chemistry. Herein, the syntheses, spectral and structural characterization of heretofore anonymous terphenylene unit (o-p-o) incorporated calixphyrin with fused sp2meso carbons is reported. The explicitly tailored macrocyclic core is utilized to stabilize the Cu(II) metal ion. The molecular structures of the calixbenziphyrin and Cu(II) complex are unambiguously confirmed by single-crystal X-ray analysis. Moreover, theoretical supports uphold experimental conclusions.

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The (o‐p‐o)‐Terphenyl Embedded Calix[2]phyrin(2.2. 1 .1. 1 ) and Its Cu(II) Complex

The introduction of a higher arene unit as a structural motif is unprecedented in calixphyrin chemistry. Herein, the syntheses, spectral and structural characterization of heretofore anonymous terphenylene unit (o-p-o) incorporated calixphyrin with fused sp2meso carbons is reported. The explicitl...

A benzannulated double aza[9]helicene was successfully synthesized via a one-pot oxidative fusion reaction, which was further derivatized to its N-alkylated ones. The X-ray structures showed double helical structures with overlapping terminal benzene rings. The double helicenes exhibit red-shifted absorption and fluorescence spectra compared to single azahelicene. Enantiomers of N-alkyl double aza[9]helicenes were optically resolved by HPLC. The CPL brightness of 19.2 M−1cm−1 was recorded.

 
<h2>Abstract</h2>
A benzannulated double aza[9]helicene 1 was successfully synthesized via a one-pot oxidative fusion reaction. 1 was derivatized to N-alkylated double aza[9]helicene 1-Et and 1-Bu, whose structures were determined by X-ray diffraction analysis. 1-Et and 1-Bu exhibited red-shifted absorption and fluorescence spectra compared to single aza[9]helicene. The double aza[9]helicenes were expected to have two different conformers. Consistent with solid-state structure, the chiral-isomer was estimated to be more stable by 16 kcal/mol relative to meso-isomer. Indeed, enantiomers of 1-Et and 1-Bu were optically resolved by HPLC and showed mirror-imaged CD and CPL spectra with the CPL brightness up to 19.2 M−1cm−1 for 1-Bu.

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The (o‐p‐o)‐Terphenyl Embedded Calix[2]phyrin(2.2. 1 .1. 1 ) and Its Cu(II) Complex

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Benzannulated Double Aza[9]helicenes: Synthesis, Structures, and (Chir)optical Properties

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