The structural landscape of ferrocenyl polychalcogenides

• Published in: Journal of organometallic chemistry 2021-10, Vol.951, p.122006, Article 122006
• Main Authors: Torubaev, Yury V., Skabitsky, Ivan V., Raghuvanshi, Abhinav
• Format: Article
• Language: English
• Subjects: Chalcogen bond; ChB; Cocrystal; Ferrocenyl; HaB; Halogen bond; Intermolecular interactions; Non-covalent bonding; Polychalcogenide; Structural landscape; supramolecular
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2021.122006

•1,1’-FcSe3, Fc2Te2 and FcTe-TeI2Fc (Fc = ferrocenyl) co-crystallize with organic HaB donor.•Resulting cocrystals are stabilized by Se•••Se, I•••Se and I•••Te HaBs and Cp•••C6F4I2 π-π interactions.•Packing patterns of the cocrystals can be inherited from the parent crystals (FcTeTeI2Fc) or governed only by HaB directionality (1,1’-FcSe3 and Fc2Te2).•Crystal and electronic structure of the cocrystals was studied by SC-XRD and in silico (DFT / NBO). Halogen bond (HaB) assisted co-crystallization strategy was used to explore the structural landscape of ferrocenic polychalcogenides varying from a rather compact ferrocenophane triselenide (1,1’-FcSe3) to bulky diferrocenyl ditelluride (Fc2Te2) and its mixed-valent derivative (FcTeTeI2Fc). Comparison of the supramolecular organization in their native crystals and respective cocrystals with the iconic halogen bond donor, 1,4-diiodotetrafluorobenzene (p-DITFB), demonstrate three different patterns: 1) conservation of the chain structures for FcTeTeI2Fc, 2) transformation of single Se···Se intermolecular interaction to double for FcSe3, and 3) for Fc2Te2, in the absence of specific and directed intermolecular interactions, the cocrystal packing of Fc2Te2 is governed only by p-DITFB HaBs directionality. This allows a rough glimpse of ferrocenic polychalcogenides structural landscape and shows the directions and methods for its further detailization. [Display omitted]