Control of Aromaticity and cis‐/trans‐Isomeric Structure of Non‐Planar Hexaphyrin(2.1.2.1.2.1) and Metal Complexes. Issue 36 (1st August 2019)

• Record Type: Journal Article
• Authors: Xue, Songlin; Kuzuhara, Daiki; Aratani, Naoki; Yamada, Hiroko
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 36(2019)
• Page Start: 12524
• Page End: 12528
• Publication Date: 2019-08-01
• Subjects: aromaticity conversion -- distorted porphyrins -- isomerization -- metal complexes -- porphyrinoids; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201906946
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Vinylene‐bridged hexaphyrin(2.1.2.1.2.1) was synthesized from dipyrrolyl diphenylethenes by acid‐catalyzed condensation reactions. Freebase hexaphyrin(2.1.2.1.2.1) forms a distorted structure with non‐aromatic characteristics. The aromaticity and molecular configuration of non‐planar hexaphyrin(2.1.2.1.2.1) can be controlled by insertion of metal ions. Freebase and zinc complexes show a distorted structure without macrocyclic aromaticity, whereas copper complexes show a figure‐of‐eight structure with macrocyclic aromaticity. It is the first example of aromaticity conversion of a distorted expanded porphyrin involving vinylene bridges. Abstract : A vinylene‐bridged hexaphyrin (Hex) was synthesized. The aromaticity and molecular configuration of non‐planar Hex can be controlled through the insertion of zinc and copper ions. The zinc complex forms a distorted non‐aromatic structure, whereas copper complexes show a figure‐of‐eight structure with macrocyclic aromaticity. This is the first example of aromaticity conversion of distorted expanded porphyrins involving vinylene bridges.