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ABSTRACT:The Au(I)-Au(I) closed-shell or aurophilic attraction has been the subject of interest in the experimental and theoretical chemistry fields, due to the intriguing properties associated to it. The presence of phosphorescence in ''aurophilic'' compounds has been addressed to a wide range of applications, but it has not yet been fully understood. A theoretical study on the electronic and phosphorescent properties of the following series of dinuclear gold complexes has been performed: [Au 2 (dmpm) (i-mnt)] (1), [Au 2 (l-Me-TU) (l-dppm)] (2), and [Au 2 (l-G)(l-dmpe)] (3). Full geometry optimizations at the second-order Møller-Plesset perturbation theory (MP2) were carried out for each of the species. These calculations made evident that, at the groundstate geometry, the Au(I) cations allocated at the center of the ring show a short Au-Au distance below the sum of the van der Waals radii, at the range of the aurophilic attraction. An intermolecular Au(I)-Au(I) closed-shell attraction for a pair of the systems under study is found. This attraction is comparable to that of the hydrogen bonds. The phosphorescent properties experimentally observed for this series were also characterized through ab initio techniques. The obtained results allow to fit reasonably

An ab initio, systematic study on the aromaticity involving the group of metalated extended porphyrins, termed meso‐hexakis(pentafluorophenyl)‐substituted[26]hexaphyrin(1.1.1.1.1.1) (HP), was performed for the first time. The aromatic behavior of the system shifted to antiaromatic in the [28]HP analogue, due to the presence of hydrogen atoms that break the orbital symmetry. The absorption bands observed in the experiment were assigned to an intraligand charge transfer, where the intrametallic character is also important. The excited states reveal the absorption of visible light and the possibility of electronic transfer to different systems. We propose a system such as single‐walled carbon nanohorns (SWCNHs), due to their special electronic properties, and predict a novel nanohybrid material. The evidence of electronic communication between both species is presented in this work. The HP aromaticity and the spatial configuration of the interaction with SWCNHs are also related to the strength of electronic transfer among the systems, making the HP metalated antiaromatic species and their corresponding nanohybrids potential candidates to be used as building blocks in photovoltaic cell materials. © 2012 Wiley Periodicals, Inc.