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Publikacja w ramach programu Royal Society of Chemistry "Gold for Gold" 2014 finansowanego przez Uniwersytet Łódzki 2 Abstract It was r ecently postulated that the benzene ring and its 4n+2 π - electron analogues are resistant to the substituent effect due to the fact that such systems tend to keep its delocalized character. Therefore, the 4n π - electron dicationic form of benzene should appear to be less resistant to the substituent effect, as compar ed with its parent neutral molecule. For this reason the effect of substitution on the dicationic form of benzene was thoroughly investigated and the consequences of single and double substitution (of par a - and meta - type) were assessed by means of several parameters, including various aromaticity indices and the Substituent Effect Stabilization Energy (SESE) parameter. It is shown that, as distinct from neutral benzene, its dicationic form is much more sensitive to the substitution. However, the dicationic benzene itself, as a moiety revealing a significant defici t of electrons, wi ll be considered as a strongly electron - withdrawing cent re , thus, interacting in a cooperative way with electron - donating substituents, and in an anticooperative way with electron - withdrawing substituents. The clear difference between sin glet - and triplet - state dicationic forms of benzene were also found. Triplet state structures seem to be significantly more delocalized, and in consequence less sensitive to the substituent effect than the singlet state structures. Finally, the para - and m eta - type substitution was investigated and it was found that the disubstituted dicationic benzene exhibits significantly different behaviour from that of neutral benzene. Although the difference between para - and meta - substitution can be found for dication ic benzene, the mechanism responsible for such an observation is differ ent than from that present in neutral benzene. Finally, it is shown how and why double ionization of benzene reduces its aromatic character in the singlet dication whereas aromaticity i s essentially conserved in the triplet dication. The above findings highlight that in the case of charged analogues of benzene the aromaticity indices can be misleading and are to be used with great precaution.

It was recently postulated that the benzene ring and its 4n + 2 p-electron analogues are resistant to the substituent effect due to the fact that such systems tend to retain their delocalized character. Therefore, the 4n p-electron dicationic form of benzene should appear to be less resistant to the substituent effect, as compared with its parent neutral molecule. For this reason the effect of substitution on the dicationic form of benzene was thoroughly investigated and the consequences of single and double substitution (of para- and meta-type) were assessed by means of several parameters, including various aromaticity indices and the Substituent Effect Stabilization Energy (SESE) parameter. It is shown that, distinct from neutral benzene, its dicationic form is much more sensitive to the substitution. However, the dicationic benzene itself, as a moiety with a significant deficit of electrons, will be considered as a strongly electron-withdrawing centre, thus interacting in a cooperative way with electron-donating substituents and in an anticooperative way with electron-withdrawing substituents. Clear differences between singlet- and triplet-state dicationic forms of benzene were also found. Triplet state structures seem to be significantly more delocalized, and as a consequence less sensitive to the substituent effect than the singlet state structures. Finally, the para- and meta-type substitution was investigated and it was found that the disubstituted dicationic benzene exhibits significantly different behaviour from that of neutral benzene. Although the difference between para- and meta-substitution can be found for dicationic benzene, the mechanism responsible for such an observation is different from that present in neutral benzene. Finally, it is shown how and why double ionization of benzene reduces its aromatic character in the singlet dication whereas aromaticity is essentially conserved in the triplet dication. The above findings highlight that in the case of charged analogues of benzene the aromaticity indices can be misleading and are to be used with great precaution. MP, MD and JD acknowledge the financial support from National Science Centre of Poland (Grant no. 2011/03/B/ST4/01351). J.D. additionally acknowledges the financial support from University of Ło´dz´ Foundation (University of Ło´dz´ Foundation Award) and from the National Science Centre of Poland (Grant no. 2012/05/N/ ST4/00203). F.M.B. thanks the Netherlands Organization for Scientific Research (NWO) for financial support. Calculations using the Gaussian 09 set of codes were carried out in Academic Computer Center Cyfronet AGH Krako´w (http://www.cyfronet. krakow.pl) and Wrocław Center for Networking and Supercomputing (http://www.wcss.wroc.pl). Access to HPC machines and licensed software is gratefully acknowledged.