Initial Report on Molecular and Electronic Structure of Spherical Multiferrocenyl/tin(IV) (Hydr)oxide [(FcSn)₁₂O₁₄(OH)₆]X₂ Clusters

Abstract

Two spherical organic−inorganic ferrocene-tin (hydr)oxide clusters of general formula [(FcSn) 12 O 14 (OH) 6 ]X 2 (Fc = ferrocenyl, X = nitroso-dicyanmethanide, DCO − and benzoylcyanoxime, PCO − anions) were prepared by the direct hydrolysis of Fc 2 SnCl 2 or FcSnCl 3 precursors in the presence of light-and thermally stable Ag(DCO) or Ag(PCO) salts. Molecular structures of FcSnCl 3 Py 2 (1), Fc 2 SnCl 2 Py 2 (2), [(FcSn) 12 O 14 (OH) 6 ](DCO) 2 (3), and [(FcSn) 12 O 14 (OH) 6 ](PCO) 2 (4) were investigated by X-ray crystallography. Density function theory (DFT) and time-dependent density functional theory (TDDFT) calculations were conducted on FcSnCl 3 Py 2 , Fc 2 SnCl 2 Py 2 , and [(FcSn) 12 O 14 (OH) 6 ] 2+ compounds in order to elaborate electronic structures and assign transitions in UV−vis spectra of these systems. The DFT and TDDFT calculations suggest that the organometallic substituents in the [(FcSn) 12 O 14 (OH) 6 ] 2+ core are rather isolated from each other.

MeSi(CH2SnRO)3 (R=Ph, Me3SiCH2): Building Blocks for Triangular‐Shaped Diorganotin Oxide Macrocycles

“…In conclusion we have shown that simple tripod‐type diorganotin halides such as MeSi(CH 2 SnRI 2 ) 3 (R=Ph, Me 3 SiCH 2 ) serve as precursors for the synthesis of novel belt‐shaped molecular diorganotin oxides [MeSi(CH 2 SnRO) 3 ] n of unprecedented oktokaideka ( n =18) and trikonta ( n =30) nuclearity. The results obtained fit well into the ongoing interest in large‐sized metaloxido clusters in general [2k] and tinoxido clusters of high nuclearity in particular [5g, 6b, 12, 31, 32] . The concept shown herein holds great potential for future work and we encourage interested readers to step into the field.…”

MeSi(CH2SnRO)3 (R=Ph, Me3SiCH2): Bausteine für dreieckförmige Diorganozinnoxidmakrocyclen

“…Zusammenfassend haben wir gezeigt, dass einfache Dreifuß‐Typ Diorganozinnhalogenide wie MeSi(CH 2 SnRI 2 ) 3 (R=Ph, Me 3 SiCH 2 ) als Edukte für die Synthese neuartiger gürtelförmiger molekularer Diorganozinnoxide [MeSi(CH 2 SnRO) 3 ] n von bisher beispielloser oktokaideka ( n =18) und trikonta ( n =30) Nuklearität dienen. Die erhaltenen Resultate liegen im andauernden Interesse an großformatigen Metalloxoclustern im Allgemeinen [2k] und Zinnoxoclustern hoher Nuklearität im Speziellen [5g, 6b, 12, 31, 32] . Das hier vorgestellte Konzept besitzt großes Potenzial für zukünftige Arbeiten und wir ermutigen interessierte Leser es aufzugreifen.…”

Shape-Controlled Synthesis of Organometallic Microcrystal-Based Hollow Hexagonal Micromotors through Evaporation-Induced Supramolecular Self-Assembly

“…The state-of-the-art technology in supramolecular self-assembly provides chemists with a simple alternative to obtain polymer-like materials through unconventional polymeric association of small molecules . In contrast to the inflexible covalent bonds, the readily controllable noncovalent interactions within the supramolecular materials result in micro/nano architectures with unique morphologies and properties, such as self-healing properties and reversible multistimuli responsiveness. − Recently the manipulation of small-molecule-based building blocks has become a focus for fabricating functional micro-/nanostructures. − A large diversity of high-ordered supramolecular micro-/nanostructures has been achieved using various micro/nano synthesis methods, involving chemical modification of building blocks, changing solvent compositions, introducing other molecules, , external stimuli including pH, − light, redox, , temperature, , and other external fields . Among them, evaporation-induced self-assembly is a simple yet effective approach for controlling the accumulated process of nanoparticles.…”