Novel Synthetic Approach to Heteroatom Doped Polycyclic Aromatic Hydrocarbons: Optimizing the Bottom-Up Approach to Atomically Precise Doped Nanographenes.

Giacomo Biagiotti,Barbara Richichi,Stefano Cicchi,Ilaria Perini

doi:10.3390/molecules26206306

Abstract

The success of the rational bottom-up approach to nanostructured carbon materials and the discovery of the importance of their doping with heteroatoms puts under the spotlight all synthetic organic approaches to polycyclic aromatic hydrocarbons. The construction of atomically precise heteroatom doped nanographenes has evidenced the importance of controlling its geometry and the position of the doping heteroatoms, since these parameters influence their chemical–physical properties and their applications. The growing interest towards this research topic is testified by the large number of works published in this area, which have transformed a once “fundamental research” into applied research at the cutting edge of technology. This review analyzes the most recent synthetic approaches to this class of compounds.

Highlights

The isolation of a single graphene layer by Geim and Novoselov [1,2] was probably the decisive impulse for the so-called “rise of the carbon age” [3,4,5]
It is possible to assemble, in a reasonable number of steps, complex structures in which the desired number of heteroatoms, substituting C=C bonds with isosteric or isoelectronic X=C or X=Y bonds, are in the desired positions and with a strict control on the geometry of the edges. This approach is an evolution of a work started decades ago dedicated to polycyclic aromatic hydrocarbons (PAHs) and has cast a new light on this subject
B-O and B-S Doped Polycyclic Aromatic Hydrocarbons Embedding Miscellaneous Rings Concerning B, O doped PAHs, a novel example of hetero substituted pentacene is offered by the synthesis of compound 160 (Figure 8) in which the 5,12-dibora-5,12dihydropentacene core is stabilized and made accessible by the presence of oxygen bridges

Summary

Introduction

The isolation of a single graphene layer by Geim and Novoselov [1,2] was probably the decisive impulse for the so-called “rise of the carbon age” [3,4,5]. An alternative and successful strategy is the use of a rational synthetic approach in which the starting material consists of molecular precursors that are assembled and transformed following a synthetic project In this way, it is possible to assemble, in a reasonable number of steps, complex structures in which the desired number of heteroatoms, substituting C=C bonds with isosteric or isoelectronic X=C or X=Y bonds, are in the desired positions and with a strict control on the geometry of the edges. It is possible to assemble, in a reasonable number of steps, complex structures in which the desired number of heteroatoms, substituting C=C bonds with isosteric or isoelectronic X=C or X=Y bonds, are in the desired positions and with a strict control on the geometry of the edges In this respect, this approach is an evolution of a work started decades ago dedicated to polycyclic aromatic hydrocarbons (PAHs) and has cast a new light on this subject. On-surface polymerization techniques were selected when they led to the formation of interesting structural patterns

N-Doped Polycyclic Aromatic Hydrocarbons

N-Doped Polycyclic Aromatic Hydrocarbons Embedding Pyridine Rings

B-Doped Polycyclic Aromatic Hydrocarbons

P or S-Doped Polycyclic Aromatic Hydrocarbons

Findings

Conclusions and Future Perspective