En Route Towards the Control of Luminescent, Optically‐Active 3D Architectures. Issue 2 (3rd November 2020)

• Record Type: Journal Article
• Authors: Hindenberg, Philip; Rominger, Frank; Romero‐Nieto, Carlos
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 2(2021)
• Page Start: 766
• Page End: 773
• Publication Date: 2020-11-03
• Subjects: 3D molecular arrangement -- Main group chemistry -- optical properties -- organophosphorus materials -- phosphorus heterocycles; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202011368
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: π‐Extended systems are key components for the development of future organic electronic technologies. While conceiving molecules with improved properties is fundamental for the evolution of materials science, keeping control over the 3D arrangement of molecules represents an ever‐expanding challenge. Herein, a synthetic protocol to replace carbon atoms of π‐systems by dissymmetric phosphorus atoms is reported; in particular, it allowed for conceiving new fused phosphapyrene derivatives with improved properties. The presence of dissymmetric phosphorus atoms precluded the formation of excimers. X‐ray diffraction revealed that, meanwhile, strong intermolecular interactions are taking place in the solid state. The phosphapyrenes photoluminesce in the visible region with high quantum yields; importantly, they are CD‐active. In addition, the unique non‐planar features of phosphorus atoms allowed for the control of the 3D arrangement of molecules, rendering lemniscate‐like structures. Based on our discoveries, we envisage the possibility to construct higher‐order, chiral 3D architectures from larger phosphorus‐containing π‐systems. Abstract : A synthetic method to replace carbon atoms of π‐extended systems by dissymmetric phosphorus centers was developed. It allowed to conceive optically active, luminescent phosphapyrenes whose dissymmetric phosphorus atoms could be employed as cornerstone to keep control over the 3D arrangement of molecules