Electronic structures of bisnoradamantenyl and bisnoradamantanyl dications and related species

Firme, Caio Lima; Costa, Tamires Ferreira da; Penha, Eduardo Tanoue da; Esteves, Pierre M.

doi:10.1007/s00894-013-1785-0

Cited by 4 publications

(12 citation statements)

References 50 publications

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“…However, this division was not shown explicitly in the D3BIA formula and yielded very small values for D3BIA. Thus, this normalization of D3BIA values was avoided in subsequent works [36,41], including this latest study.…”

Section: D3bia General Formulamentioning

confidence: 99%

“…We have previously validated D3BIA for the analysis of homoaromaticity [36] and sigma aromaticity [21], but as mentioned above, no validation of D3BIA for benzenoid systems has been achieved to date. Thus, a new study is necessary to prove that D3BIA can be used for benzenoid systems, e.g., acenes.…”

Section: D3bia General Formulamentioning

confidence: 99%

“…Like all other aromaticity indices, the D3BIA is an arbitrary aromaticity index, but has the advantage that it can be applied to all aromatic and homoaromatic systems with or without heteroatoms and it has no reference parameter. Early works have shown that D3BIA has very good correlation with NICS for a set of homoaromatic bisnoradamantenyl derivatives [36] and tetrahedranes derivatives [21]. However, no previous work has shown that D3BIA can be used to quantify the aromaticity of benzenoid systems.…”

Section: Introductionmentioning

confidence: 99%

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Validation of the recently developed aromaticity index D3BIA for benzenoid systems. Case study: acenes

2015

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There are four types of aromaticity criteria: energetic, electronic, magnetic and geometric. The delocalization, density and degeneracy-based index of aromaticity, D3BIA, is an electronic aromaticity index from QTAIM that is not reference dependent and can be used for aromatic, homoaromatic, sigma aromatic and other aromatic systems with varying ring size containing hetereoatoms or not. We used B3LYP, MP2 and MP3 methods to search for linear relations between well-known aromaticity indices and D3BIA for a series of acenes. We found that the D3BIA versus FLU correlation exceeded 91 % and reasonably good correlations exist between D3BIA and HOMA and between D3BIA and PDI. Previous works have shown that D3BIA can be used for homoaromatic systems and tetrahedrane derivatives (sigma aromaticity), but no previous work has validated D3BIA for benzenoid systems. This is the first time we have shown that D3BIA can be used successfully for benzenoid systems, for example, acenes. This work supports and validates the use of D3BIA in classical aromatic systems.

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Section: D3bia General Formulamentioning

confidence: 99%

Section: D3bia General Formulamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Validation of the recently developed aromaticity index D3BIA for benzenoid systems. Case study: acenes

2015

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“…Firme et al used the D3BIA index and the nucleus‐independent chemical shift (NICS) to study the electronic structure of bisnoradamantenyl and bisnoradamantanyl cations and some of their derivatives. The D3BIA and NICS indicators display a linear correlation for the examined species.…”

Section: Applications Of Qtaimmentioning

confidence: 99%

Latin American contributions to quantum chemical topology

García‐Revilla

Cortés‐Guzmán

Rocha‐Rinza

et al. 2018

Int J of Quantum Chemistry

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We survey the contributions from Latin American theoretical chemists to the field of quantum chemical topology (QCT) over nearly the last 30 years with emphasis on the developments and applications of the quantum theory of atoms in molecules (QTAIM). Applications of QCT in the fields of excited states, electron delocalization, chemical bond, aromaticity, conformational analysis, spectroscopic properties, and chemical reactivity are presented. We also consider the coupling of QTAIM with time‐dependent density functional theory, the virial theorem in the Kohn‐Sham method and the inclusion of electron dynamical correlation in the interacting quantum atoms method using coupled cluster and multi‐configurational densities. Additionally, we describe the development of efficient algorithms for the calculation of topological properties derived from the electron density. This review is aimed not only at providing an account of the contributions to QCT in Latin America but also at stimulating guides for further progress in the field.

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“…Apart from the consistency dilemma, aromaticity indexes (and/or concepts) have been used to understand an interminable list of intricate chemical structures [13], such as the families of bisnoradamantenyl dications [14], tetrahedranes [15], cyclophanes [16], all-metal aromatic clusters [17], caged structures with spherical aromaticity [18], structures with supramolecular aromaticity [19], carbo-aromatic compounds [20], etc.…”

Section: Introductionmentioning

confidence: 99%

D2BIA—flexible, not (explicitly) arbitrary and reference/structurally invariant—a very effective and improved version of the D3BIA aromaticity index

Firme

Araújo

2017

J Mol Model

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Although there are a multitude of aromaticity indexes, only a few have a widespread usage. All famous aromaticity indexes are limited: HOMA and FLU are reference-dependent; ELF is π-bond-dependent; PDI is structurally dependent and NICS is ring size dependent. These limitations stimulate the continuous search for better (i.e., having no dependency), more flexible (i.e., applied to any aromatic system) and more effective (i.e., with excellent correlations with other indexes) aromaticity indexes. The D3BIA was our first topological aromaticity index. It is flexible, reference-independent and effective for planar and caged aromatic molecules. However, one of its terms, the degree of degeneracy (δ), is arbitrary and difficult to carry out for new users. Thus, in this work, we show that D2BIA-an improved version of D3BIA-is a good candidate to be used widely, since it retains the strong points of D3BIA while avoiding its weak point. In particular cases where all studied systems have δ = 1 (e.g., for acenes), then D2BIA equals D3BIA. For our recent study with acenes, D3BIA (and, as a consequence, D2BIA) has (have) an excellent correlation with FLU according to the MP3 method. In this work, by using DFT calculations for a series involving several six-membered and five-membered heteroaromatic rings, only D2BIA and NICS have very good correlation. All other well known aromaticity indexes used in this work (FLU, HOMA and ELF) gave poor correlations. As to homoaromatic systems, only D2BIA vs NICS and D2BIA vs FLU plots have excellent correlations. HOMA has the worst results in this series. Thus, D2BIA proved to be flexible and effective for the analysis of heteroaromatic rings of different sizes and for caged homoaromatic systems. Moreover, D2BIA has better correlations than D3BIA for planar aromatic systems, and same correlations for caged-homoaromatic systems. Graphical abstract D2BIA-an effective and improved version of the D3BIA aromaticity index.

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Electronic structures of bisnoradamantenyl and bisnoradamantanyl dications and related species

Cited by 4 publications

References 50 publications

Validation of the recently developed aromaticity index D3BIA for benzenoid systems. Case study: acenes

Validation of the recently developed aromaticity index D3BIA for benzenoid systems. Case study: acenes

Latin American contributions to quantum chemical topology

D2BIA—flexible, not (explicitly) arbitrary and reference/structurally invariant—a very effective and improved version of the D3BIA aromaticity index

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