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Substituent Effects on Crosslike Packing of 2′,7′-Diaryl- spiro(cyclopropane-1,9′-fluorene) Derivatives: Synthesis and Crystallographic, Optical, and Thermal Properties

Authors


  • P.L. thanks the National Natural Science Foundation of China (20374045) and the Natural Science Foundation of Zhejiang Province. Supporting Information is available online from Wiley InterScience or from the author.

Abstract

A series of 2′,7′-diarylspiro(cyclopropane-1,9′-fluorene) derivatives are efficiently synthesized and characterized to determine the reason for the “green-light” emission of these compounds. These compounds exhibit bright-violet to blue photoluminescence (PL) (λPLmax = 353–419 nm) with excellent PL quantum efficiencies (ΦPL = 83–100 %) in solution and show high thermal stabilities (Td = 267–474 °C). The variation of the optical properties of these molecules in the solid state depends on the different stacking modes of these compounds containing different substituents, which are revealed by crystallographic analysis. CH…π hydrogen bonds instead of intermolecular π–π interactions act as the driving force between adjacent fluorenes, even though a very small dialkyl group (cyclopropane) is introduced at the C-9 position of fluorene. The crosslike molecular stacking efficiently reduces the energy transfer between the herring-like aggregates and therefore results in the absence of a “green-light” emission tail. In order to determine the cause of the “green-light” emission tails, the fluorescence spectra of the films annealed in N2 or in air are recorded. Broad green-light emission tails were observed for the films annealed in air, which might be caused by fluorenone defects generated during processing or during the course of the photophysical analysis by reaction with residual oxygen.

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