Understanding the reactivity of polycyclic aromatic hydrocarbons and related compounds

Abstract

This perspective article summarizes recent applications of the combined activation strain model of reactivity and the energy decomposition analysis methods to the study of the reactivity of polycyclic aromatic hydrocarbons and related compounds.

Gas-phase synthesis of benzene via the propargyl radical self-reaction

“…The benzene molecule [C 6 H 6 (1) ] isolated 175 years ago by Hofmann ( 1 ) has been recognized as the fundamental molecular building block of polycyclic aromatic hydrocarbons (PAHs)—organic molecules composed of multiple fused benzenoid rings ( Fig. 1 ) ( 2 ). PAHs, along with their protonated ( 3 ), ionized ( 4 ), alkylated ( 5 ), and (de)hydrogenated ( 6 ) counterparts, are ubiquitous in the universe and have been associated with the unidentified infrared emission bands ( 7 – 9 ) and with the diffuse interstellar bands (DIBs)—discrete absorption features superimposed on the interstellar extinction curve ( 9 , 10 ).…”

Rationalizing the AlI‐Promoted Oxidative Addition of C−C Versus C−H Bonds in Arenes

“…For this reason, we decided to gain ad etailed quantitative insight on this novel transformation mainly by meanso ft he combination of the Activation Strain Model (ASM) [13] of reactivity and the EnergyD ecomposition Analysis (EDA) [14] methods. This approach has been chosen because it has not only contributedt oo ur current understanding of fundamental reactions in organic, [15] organometallic, [16] and main group [17] chemistry but also because it has been particularly helpfult o analyze the physical factorsc ontrolling oxidative addition reactions mediated by either transition metal complexes [18] or group 13 carbenoids. [19] Issues such as the competition between the CÀCa nd CÀHa ctivation pathways involving different arenes as well as the impact of the aromaticity of either the reaction products or the transition states on the transformation should be considered herein to rationalize the ultimate factors governing these so far poorly understood reactions.…”

Unusual reversibility in molecular break-up of PAHs: the case of pentacene dehydrogenation on Ir(111)

“…The chemical reactivity of acenes (polycyclic aromatic hydrocarbons, PAHs, composed by linearly fused benzene rings) has attracted the interest of the scientific community for their application in the field of organic electronics 1 . In this respect, benzene, naphthalene, and anthracene are by far the the most studied organic molecules.…”

“…The chemical reactivity of acenes (polycyclic aromatic hydrocarbons, PAHs, composed of linearly-fused benzene rings) has attracted the interest of the scientific community for their application in the field of organic electronics. 1 In this respect, benzene, naphthalene, and anthracene are by far the most studied organic molecules. Pentacene, consisting of five linearly-fused benzene rings, has received extensive attention being an active semiconducting material with a very large charge-carrier mobility.…”