密度泛函理论研究奈韦拉平结构,芳香性和电荷性质

利用密度泛函理论(DFT)和Hartree-Fock方法,分别在B3LPY/6-31G和HF/6-31G基组水平上优化了奈韦拉平的几何和电子结构.从奈韦拉平的几何结构出发,分析了其稳定性、芳香性和电子结构特性.计算结果表明,C_1点群对称性为基态奈韦拉平结构.对于奈韦拉平,芳香性大小按环4环3环1的顺序依次降低;环1、环3、环4具有芳香性,环2具有反芳香性.氮原子和碳原子形成sp~2杂化,氧原子形成sp杂化.     

Aromatization of triafulvene and its exocyclic Si,Ge, and Sn derivations by complexation with halogen atoms

The geometries of triafulvene (TF) and its exocyclic Si, Ge, and Sn analogues complexes with F, Cl, Br, and I halogen atoms (TF(X)···Y, X═C, Si, Ge, and Sn; Y═F, Cl, Br, and I) were studied. The complexes were optimized at DFT(B3LYP)/6–311+G(d,p) level of theory. To assess the aromaticity of the considered complexes the geometry-based (HOMA), magnetism-based (NICS), and recently introduced electronic-based (electric field gradient (EFG(0); Shannon aromaticity (SA)) aromaticity indices were employed. The increasing tendency of aromaticity in each complex species was noted as the series of TF(X)···F > TF(X)···Cl > TF(X)···Br > TF((X)···I. Then, the binding energies corrected by basis set super position error (BSSE) were calculated by single point energy calculations at M06-2X/6-311+G(d,p) level. Natural bond orbital (NBO) analysis confirmed that the charge transfer takes place from TF(X) to the halogen atoms. Some topological parameters, within the framework of the quantum theory of atoms in molecules (QTAIM), were also calculated to estimate the aromaticity of the complexes. It was seen that there are some important correlations between the topological parameters and aromaticity indices. In addition the most striking finding was that all the TF(X) molecules are connected with the halogen atoms through Y···C1═C2 (π) noncovalent interaction. This interaction was also investigated through noncovalent interaction (NCI) analysis.     

Paramagnetic ring current effects in anti-aromatic structures subject to substitution/annelation quantified by spatial magnetic properties (TSNMRS)

The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of the typically anti-aromatic cyclopentadienyl cation, cyclobutadiene, pentalene, s-indacene and of substituted/annelated analogues of the latter structures have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to visualize and quantify the dia(para)magnetic ring current effects in the studied compounds. The interplay of dia(para)magnetic ring current effects due to substitution/annelation caused by heavy exo-cyclic n,π-electron delocalization can be qualified.     

Stability and reactivities based on moment analysis

The truncated expansion of a function ¦x¦ is used to obtain the total Hückel -electron energy partitioned into various sums, in terms of moments as well as molecular fragments. The additivity is in general satisfactory for acyclic and cyclic systems, which exhibit a regularity called the generalized Hückel rule which indicates whether a fragment plays the role of stabilization or of destabilization. A unified treatment based on the energy partitioning is proposed for rationalizing aromaticity, reactivities and bond lengths of conjugated hydrocarbons. The relationships between molecular properties and topology can be deduced from inspecting, enumerating or summing the relative contributions of various fragments. Also known as: Yuan-sun Kiang     

分子中芳香性自动识别算法

以图论为基础,从化合物的二维连接表出发,在环识别算法的约束下,对分子中的节点进行判断。结果表明,该算法能够识别大多数化合物中的芳香性。作为约束条件,把芳香性的识别算法应用于ESESOC系统中结构的穷举生成,得到了较好的结果。     

自然键轨道方法研究分子的芳香性

用自然键轨道方法研究了环状共轭分子的芳香性,提出了用自然键轨道的准离域能作为量度分子芳香性的标准,用INDO方法和DV-Xα方法计算了20多个环状有机或无机分子的自然键轨道的准离域能。根据准离域能标准判断的分子芳香性大小顺序与文献的结果基本一致,表明本文提出的芳香性量度标准的有效性和可用性。     

Aromatic patterns: Tryptophan aromaticity as a catalyst for the emergence of life and rise of consciousness

Sunlight held the key to the origin of life on Earth. The earliest life forms, cyanobacteria, captured the sunlight to generate energy through photosynthesis. Life on Earth evolved in accordance with the circadian rhythms tied to sensitivity to sunlight patterns. A unique feature of cyanobacterial photosynthetic proteins and circadian rhythms' molecules, and later of nearly all photon-sensing molecules throughout evolution, is that the aromatic amino acid tryptophan (Trp) resides at the center of light-harvesting active sites. In this perspective, I review the literature and integrate evidence from different scientific fields to explore the role Trp plays in photon-sensing capabilities of living organisms through its resonance delocalization of π-electrons. The observations presented here are the product of apparently unrelated phenomena throughout evolution, but nevertheless share consistent patterns of photon-sensing by Trp-containing and Trp-derived molecules. I posit the unique capacity to transfer electrons during photosynthesis in the earliest life forms is conferred to Trp due to its aromaticity. I propose this ability evolved to assume more complex functions, serving as a host for mechanisms underlying mental aptitudes – a concept which provides a theoretical basis for defining the neural correlates of consciousness. The argument made here is that Trp aromaticity may have allowed for the inception of the mechanistic building blocks used to fabricate complexity in higher forms of life. More specifically, Trp aromatic non-locality may have acted as a catalyst for the emergence of consciousness by instigating long-range synchronization and stabilizing the large-scale coherence of neural networks, which mediate functional brain activity. The concepts proposed in this perspective provide a conceptual foundation that invites further interdisciplinary dialogue aimed at examining and defining the role of aromaticity (beyond Trp) in the emergence of life and consciousness.     

Bonding Character,Electron Delocalization,and Aromaticity of Cyclo[18]Carbon (C18) Precursors,C18-(CO)n (n=6, 4, and 2): Focusing on the Effect of Carbonyl (-CO) Groups**

The bonding character, electron delocalization, and aromaticity of the cyclo[18]carbon (C₁₈) precursors, C₁₈-(CO)_n (n=6, 4, and 2), have been studied by combining quantum chemical calculations and various electronic wavefunction analyses with different physical bases. It was found that C₁₈-(CO)_n (n=6, 4, and 2) molecules exhibit alternating long and short C−C bonds, and have out-of-plane and in-plane dual π systems (π^out and πⁱⁿ) perpendicular to each other, which are consistent with the relevant characteristics of C₁₈. However, the presence of carbonyl (-CO) groups significantly reduced the global electron conjugation of C₁₈-(CO)_n (n=6, 4, and 2) compared to C₁₈. Specifically, the -CO group largely breaks the extensive delocalization of πⁱⁿ system, and the π^out system is also affected by it but to a much lesser extent; as a consequence, C₁₈-(CO)_n (n=6, 4, and 2) with larger n shows weaker overall aromaticity. Mostly because of the decreased but still apparent π^out electron delocalization in the C₁₈-(CO)_n (n=6, 4, and 2), a notable diatropic induced ring current under the action of external magnetic field is observed, demonstrating the clear aromatic characteristic in the molecules. The correlation between C₁₈-(CO)_n (n=6, 4, and 2) and C₁₈ in terms of the gradual elimination of -CO from the precursors showed that the direct elimination of two CO molecules in C₁₈-(CO)_n (n=6, 4, and 2) has a synergistic mechanism, but it is kinetically infeasible under normal conditions due to the high energy barrier.