Simple Perylene Diimide Cyclohexane Derivative With Combined CPL and TPA Properties

Pablo Reine; Ana M Ortuño; Inês F A Mariz; Maria Ribagorda; Juan M Cuerva; Araceli G Campaña; Emerlinda Maçôas; Delia Miguel

doi:10.3389/fchem.2020.00306

Simple Perylene Diimide Cyclohexane Derivative With Combined CPL and TPA Properties

Front Chem. 2020 Apr 21:8:306. doi: 10.3389/fchem.2020.00306. eCollection 2020.

Authors

Pablo Reine¹, Ana M Ortuño¹, Inês F A Mariz², Maria Ribagorda³, Juan M Cuerva¹, Araceli G Campaña¹, Emerlinda Maçôas², Delia Miguel⁴

Affiliations

¹ Departamento de Química Orgánica, Facultad de Ciencias, Unidad de Excelencia de Química Aplicada a Biomedicina y Medioambiente (UEQ), Universidad de Granada, Granada, Spain.
² Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Lisbon, Portugal.
³ Departamento de Química Orgánica, Facultad de Ciencias, C.U. Cantoblanco, Universidad Autónoma de Madrid, Madrid, Spain.
⁴ Departamento de Fisicoquímica, Facultad de Farmacia, UEQ, Universidad de Granada, Granada, Spain.

Abstract

In this work we describe the linear and non-linear (chiro)optical properties of an enantiopure bis-perylenediimide (PDI) cyclohexane derivative. This compound exhibits upconversion based on a two-photon absorption (TPA) process with a cross-section value of 70 GM together with emission of circularly polarized luminescence (CPL), showing a g_lum in the range of 10^-3. This simple structure represents one of the scarce examples of purely organic compounds combining both TPA and CPL responses, together with large values of molar absorptivity and fluorescence quantum yield with emission in the 500-600 nm. Self-assembly induced by introduction of a poor solvent allows for a spectacular shift of the emission into the near-infrared (NIR, 650-750 nm) by formation of well-defined rotationally displaced dimers. Therefore, we are here presenting a versatile platform whose optical properties can be simply tuned by self-assembly or by functionalization of the electron-deficient aromatic core of PDIs.

Keywords: circularly polarized luminiscence (CPL); electronic circular dichroism (ECD); non-linear emission; perylene diimide (PDI); two-photon absorption.