Structural Manipulation of the Conjugated Phenyl Moiety in 3-Phenylbenzofulvene Monomers: Effects on Spontaneous Polymerization.

Marco Paolino,Giorgio Grisci,Alessandro Grillo,Vincenzo Razzano,Annalisa Reale,Raniero Mendichi,Antonella Boccia,Daniele Piovani,Gianluca Giorgi,Andrea Cappelli,Germano Giuliani,Alessandro Donati

doi:10.3390/polym10070752

Marco Paolino, Giorgio Grisci + Show 10 more

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https://doi.org/10.3390/polym10070752

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Abstract

Spontaneous polymerization is an intriguing phenomenon in which pure monomers begin their polymerization without initiators or catalysts. Previously, 3-phenylbenzofulvene monomers were found to polymerize spontaneously after solvent removal. Here, eight new 3-substituted benzofulvene monomers 1a–h were synthesized in order to investigate the effects of differently substituted aromatic rings in position 3 of the benzofulvene scaffold on spontaneous polymerization. The newly synthesized monomers maintained the tendency toward spontaneous polymerization. However, monomer 1a, bearing an ortho-methoxy substituted phenyl, polymerized hardly, thus producing low polymerization yields, inhomogeneous structure, and low molecular weight of the obtained polymeric material. This result suggested the importance of the presence of hydrogen atoms in the 2′-position to achieve productive interactions among the monomers in the recognition step preluding the spontaneous polymerization and among the monomeric units in the polybenzofulvene backbones. Moreover, this study paves the way to modify the pendant rings in position 3 of the indene scaffold to synthesize new polybenzofulvene derivatives variously decorated.

Highlights

Spontaneous polymerization is an intriguing phenomenon in which pure monomers begin their polymerization without initiators or catalysts
We have previously proposed for the phenyl ring in position 3 of the indene nucleus a pivotal role in the spontaneous polymerization of our benzofulvene monomers
In this paper, we report on the synthesis and the characterization of eight new 3-substituted benzofulvene monomers variously substituted on the pendant phenyl ring and of the corresponding polymeric materials

Summary

Introduction

Spontaneous polymerization is an intriguing phenomenon in which pure monomers begin their polymerization without initiators or catalysts. This study paves the way to modify the pendant rings in position 3 of the indene scaffold to synthesize new polybenzofulvene derivatives variously decorated. Thanks to their mechanical property, low intrinsic cost, and the ability to manipulate its structure, they are used in the development of organic light-emitting diodes (OLEDs) [5,6], solar and photovoltaic cells [7,8], and sensors and field effect transistors (FETs) [9,10]. A similar type of intrachain stacking has been proposed to affect type of intrachain has been proposed to affect the properties of some fulvene (FV) derivative the properties of stacking some fulvene (FV)

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