Based on the local Shannon entropy concept in information theory, a new measure of aromaticity is introduced. This index, which describes the probability of electronic charge distribution between atoms in a given ring, is called Shannon aromaticity (SA). Using B3LYP method and different basis sets (6-31G**, 6-31+G** and 6-311++G**), the SA values of some five-membered heterocycles, C(4)H(4)X, a...

It is demonstrated that the Pauli antisymmetry principle (PAP) is without influence in the 7r electron subspace of polyenes and (4n + 2) annulenes (n = 0, 1, 2...) as long as the hoppings are restricted to nearest-neighbour centers. Here the 7r electrons behave like a hard core bosonic (heb) ensemble where fermionic on-site and bosonic intersite properties are combined. In An and (In + 1) annul...

Our recent studies on the synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes are summarized. Core-modified P,X,N2-porphyrins (X = S, N) are accessible from a σ4-phosphatripyrrane and the corresponding 2,5-difunctionalized heteroles in a few steps. X-ray structural analysis of the σ-P,N3 porphyrin revealed that it possesses a slightly distorted 18...

A series of tentative single-molecule conductance switches which could be triggered by light were examined by computational means using density functional theory (DFT) with non-equilibrium Green's functions (NEGF). The switches exploit the reversal in electron counting rules for aromaticity and antiaromaticity upon excitation from the electronic ground state (S0) to the lowest ππ* excited singl...

Replacement of halide from N-(haloboryl)formamidines for the weakly coordinating anion [B(C(6)F(5))(4)](-), using [Et(3)Si(toluene)](+)[B(C(6)F(5))(4)](-), induces a ring closure leading to the cationic four-pi-electron four-membered heterocycles [HC(N-2,6-diisopropylphenyl)(2)BR](+) [R = N(i-Pr)(2), Ph]. Subsequent deprotonation of the B-amino derivative affords the corresponding N-heterocycli...

The perfluoro- and perprotiopentaphenylboroles 1 and 2 react with dihydrogen to effect H-H bond cleavage and formation of boracyclopentene products. The mechanism of this reaction has been studied experimentally through evaluation of the kinetic properties of the slower reaction between 2 and H(2). The reaction is first-order in both [borole] and [H(2)] with activation parameters of ΔH(‡) = 34(...

Previously, we developed the deoxycytosine analog Ç (C-spin) as a bi-functional spectroscopic probe for the study of nucleic acid structure and dynamics using electron paramagnetic resonance (EPR) and fluorescence spectroscopy. To understand the effect of Ç on nucleic acid structure, we undertook a detailed crystallographic analysis. A 1.7 Å resolution crystal structure of Ç within a decamer du...

Substitution of two or four carbon atoms by nitrogen in the corannulene molecule as a carbon nanostructure was done and the obtained structures were optimized at MP2/6-31G(d) level of theory. Calculations of the nucleus-independent chemical shift (NICS) were performed to analyze the aromaticity of the corannulene rings and its derivatives upon doping with N at B3LYP/6-31G(d) level of theory. Re...