[4]Cyclo-N-alkyl-2,7-carbazoles: Influence of the Alkyl Chain Length on the Structural, Electronic, and Charge Transport Properties

Macrocycles possessing radially oriented pi-orbitals have experienced a fantastic development. However, their incorporation in organic electronic devices remains very scarce. In this work, we aim at bridging the gap between organic electronics and nanorings by reporting the first detailed structure-properties-device performance relationship study of organic functional materials based on a nanoring system. Three [4]cyclo-N-alkyl-2,7-carbazoles bearing different alkyl chains on their nitrogen atoms have been synthesized and characterized by combined experimental and theoretical approaches. This study includes electrochemical, photophysical, thermal, and structural solid-state measurements and charge transport properties investigations. An optimized protocol of the Pt approach has been developed to synthesize the [4]cyclocarbazoles in high yield (52-64%), of great interest for further development of nanorings, especially in materials science. The charge transport properties of [4]cyclocarbazoles and model compound [8]cycloparaphenylene ([8]CPP) have been studied. Although no field effect (FE) mobility was recorded for the benchmark [8]CPP, FE mobility values of ca. 10(-5) cm(2).V-1.s(-1) were recorded for the [4]cyclocarbazoles. The characteristics (threshold voltage V-TH, subthreshold swing Delta S, trapping energy ?E) recorded for the three [4]cyclocarbazoles appear to be modulated by the alkyl chain length borne by the nitrogen atoms. Remarkably, the space-charge-limited current mobilities measured for the [4]cyclocarbazoles are about 3 orders of magnitude higher than that of [8]CPP (1.37/2.78 x 10(-4) cm(2).V-1.s(-1) for the [4]cyclocarbazoles vs 1.21 x 10(-7) cm(2).V-1.s(-1) for [8]CPP), highlighting the strong effect of nitrogen bridges on the charge transport properties. The whole study opens the way to the use of nanorings in electronics, which is now the next step of their development.

Automated summary

The study investigates the relationship between the structure, properties, and device performance of organic functional materials based on nanorings, revealing the strong influence of nitrogen bridges on charge transport properties. This paves the way for the application of nanorings in electronics.