An Insight into the Local Aromaticities of Polycyclic Aromatic Hydrocarbons and Fullerenes

Poater, Jordi; Fradera, Xavier; Duran, Miquel; Solà, Miquel

doi:10.1002/chem.200390128

Cited by 150 publications

(147 citation statements)

References 124 publications

(233 reference statements)

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“…The DI value between atoms A and B, ␦(A,B), is obtained by the double integration of the exchange-correlation density over the basins of atoms A and B in the framework of the atoms in the molecules ͑AIM͒ theory of Bader ͑vide infra͒. 24 Previous works 23,25 have shown that for a series of planar and curved polycyclic aromatic hydrocarbons ͑PAHs͒, there is a satisfactory correlation between NICS, HOMA, and PDI. In general, larger PDIs go with larger absolute values of NICS and larger HOMA values.…”

Section: Introductionmentioning

confidence: 99%

The aromatic fluctuation index (FLU): A new aromaticity index based on electron delocalization

Matito

Duran

Solà

2004

The Journal of Chemical Physics

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In this work, the aromatic fluctuation index ͑FLU͒ that describes the fluctuation of electronic charge between adjacent atoms in a given ring is introduced as a new aromaticity measure. This new electronic criterion of aromaticity is based on the fact that aromaticity is related to the cyclic delocalized circulation of electrons. It is defined not only considering the amount of electron sharing between contiguous atoms, which should be substantial in aromatic molecules, but also taking into account the similarity of electron sharing between adjacent atoms. For a series of rings in 15 planar polycyclic aromatic hydrocarbons, we have found that, in general, FLU is strongly correlated with other widely used indicators of local aromaticity, such as the harmonic-oscillator model of aromaticity, the nucleus independent chemical shift, and the para-delocalization index ͑PDI͒. In contrast to PDI, the FLU index can be applied to study the aromaticity of rings with any number of members and it can be used to analyze both the local and global aromatic character of rings and molecules.

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Section: Introductionmentioning

confidence: 99%

The aromatic fluctuation index (FLU): A new aromaticity index based on electron delocalization

Matito

Duran

Solà

2004

The Journal of Chemical Physics

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400

203

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“…50,126 On the other hand, it does a good job in polycyclic aromatic hydrocarbons. 127 Ángyán 128, 129 showed the connection between the 2c-ESI and the LRK for the QTAIM partition, which suggests that the PLR and the PDI could be measuring the same effect in a molecular ring.…”

Section: Flumentioning

confidence: 99%

Quantifying aromaticity with electron delocalisation measures

et al. 2015

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Aromaticity cannot be measured directly by any physical or chemical experiment because it is not a well-defined magnitude. Its quantification is done indirectly from the measure of different properties that are usually found in aromatic compounds such as bond length equalisation, energetic stabilisation, and particular magnetic behaviour associated with induced ring currents. These properties have been used to set up the myriad of structural-, energetic-and magnetic-based indices of aromaticity known to date. Cyclic delocalisation of mobile electrons in two or three dimensions is probably one of the key aspects that characterise aromatic compounds. However, it has not been until the last decade that electron delocalisation measures have been widely employed to quantify aromaticity. Some of these new indicators of aromaticity such as the PDI, FLU, ING, and INB were defined in our group. In this paper, we review the different existent descriptors of aromaticity that are based on electron delocalisation properties, we compare their performance with indices based on other properties, and we summarise a number of applications of electronic-based indices for the analysis of aromaticity in interesting chemical problems.2

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“…Lately aromaticity measures based on the electronic structure of molecules are becoming popular, and several research groups have contributed to the issue by providing new aromaticity indices. Among others we can mention the I ring [36] of Giambiagi et al, the Six Center Index (SCI) [37] of Bultinck and coworkers, the θ of Matta, [38] the PDI of Poater et al [39] or the FLU of Matito et al [40,41]; for recent reviews see Refs. [42] and [43].…”

Section: Theorymentioning

confidence: 99%

Performance of 3D‐space‐based atoms‐in‐molecules methods for electronic delocalization aromaticity indices

et al. 2010

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Several denitions of an atom in a molecule (AIM) in three dimensional space, including both fuzzy and disjoint domains, are employed to calculate electron sharing indices (ESI) and related electronic aromaticity measures, namely Iring and multicenter indices (MCI), for a wide set of cyclic planar aromatic and non-aromatic molecules of dierent ring size. The results obtained using the recent iterative Hirshfeld scheme are compared to those derived from the classical Hirshfeld method and from Bader's quantum theory of atoms in molecules. For bonded atoms all methods yield ESI values in very good agreement, especially for C-C interactions. In the case of non-bonded interactions there are relevant deviations, particularly between fuzzy and QTAIM schemes. These discrepancies directly translate into signicant dierences in the values and the trends of the aromaticity indices. In particular, the chemically expected trends are more consistently found when using disjoint domains. Careful examination of the underlying eects reveals the dierent reasons why the aromaticity indices investigated give the expected results for binary divisions of three dimensional space.

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An Insight into the Local Aromaticities of Polycyclic Aromatic Hydrocarbons and Fullerenes

Cited by 150 publications

References 124 publications

The aromatic fluctuation index (FLU): A new aromaticity index based on electron delocalization

The aromatic fluctuation index (FLU): A new aromaticity index based on electron delocalization

Quantifying aromaticity with electron delocalisation measures

Performance of 3D‐space‐based atoms‐in‐molecules methods for electronic delocalization aromaticity indices

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