Assessing the Extent of π-Electron Delocalization in Naphtho-Annelated Fluoranthenes by Means of Topological Ring-Currents

The extent of π-electron delocalization in the five-membered rings of 14 naphtho-annelated fluoranthenes has recently been assessed by means of several approaches, including application of the following indices: the energy effect (ef), bond resonance-energy (BRE), multicenter delocalization-energies (MCI), the index arising from the harmonic-oscillator model of aromaticity (HOMA), and nucleus-independent chemical shifts (NICS). The calculated Hückel-London-Pople-McWeeny (HLPM) ("topological") ring-current intensities (TRC) for the five-membered rings of these same structures are here compared with the above-named indices in order to assess how well TRC parallels these other criteria. The indices ef and BRE are the ones that correlate best with TRC, and it is suggested that this is because all three approaches are founded on the Hückel model. TRC does not, however, confirm the proposal that cyclic delocalization in the five-membered rings can be greater than in any of the six-membered rings in this series of conjugated systems. Certain ostensible shortcomings of the NICS approach are discussed, and some doubts are emphasized regarding the legitimacy of associating "ring currents" with "aromaticity".