Chalcogen Bonding: Experimental and Theoretical Determinations from Electron Density Analysis. Geometrical Preferences Driven by Electrophilic鈥揘ucleophilic Interactions

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• 作者：Mariya E. Brezgunova ; Julien Lieffrig ; Emmanuel Aubert ; Slimane Dahaoui ; Pierre Fertey ; S茅bastien Leb猫gue ; J谩nos G. 脕ngy谩n ; Marc Fourmigu茅 ; Enrique Espinosa
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：August 7, 2013
• 年：2013
• 卷：13
• 期：8
• 页码：3283-3289
• 全文大小：425K
• 年卷期：v.13,no.8(August 7, 2013)
• ISSN：1528-7505

文摘

Chalcogen bonding has been investigated in terms of the electron density distribution 蟻(r) around chalcogen atoms. The evolution of 蟻(r) along the series of chalcogen atoms is shown based on ab initio calculations on chalcogenophthalic anhydrides C₈O₂H₄Chal (Chal = O, S, Se, and Te), where the Chal atom is in its sp³ hybridization. From a detailed analysis of the experimental and theoretical electron density and the L(r) = 鈭?img src="/appl/literatum/publisher/achs/journals/entities/2207.gif" alt="" class="entityA" align="absbottom" />²蟻(r) function in the crystal phase of C₈O₂H₄Se, we characterize directionality and strength of chalcogen bonding (Se路路路O and Se路路路Se) and hydrogen bonding (Se路路路H) interactions. In addition, several isolated dimers and a trimer of C₈O₂H₄Se have been also studied at the X-ray geometry in order to compare interaction energies with those estimated from the measured electron density. Similarly to halogen atoms in halogen bonding interactions, the anisotropic distribution of 蟻(r) around the Chal atoms was found to be at the origin of chalcogen bonding. Therefore, the concepts, developed earlier for halogen bonding, are extended here to chalcogen bonding interactions. From the results of this work, the L(r) function proves to be more precise than the 蟽-hole concept to identify electrophilic sites of Se-atoms in sp³ hybridization.