Experimental and Theoretical Studies of a Spirostannole and Formation of a Pentaorganostannate

• Published in: Molecules (Basel, Switzerland) Switzerland), 2020-10, Vol.25 (21), p.4993
• Main Authors: Ramirez Y Medina, Isabel-Maria, Rohdenburg, Markus, Kipke, Waldemar, Lork, Enno, Staubitz, Anne
• Format: Article
• Language: English
• Subjects: Absorption; density functional calculations; Density Functional Theory; Emission spectra; Emitters; Geometry; Lithium; Magnetic resonance spectroscopy; main group chemistry; Maxima; Models, Molecular; Molecular Conformation; Molecular orbitals; Molecular structure; NMR; NMR spectroscopy; Nuclear magnetic resonance; Organometallic Compounds - chemistry; organometallics; Pollution monitoring; spiro compounds; Spiro Compounds - chemistry; stannoles
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules25214993

A new spirostannole, 1,1',3,3'-tetrakis(5-methylthiophen-2-yl)-4,4',5,5',6,6',7,7'-octahydro-2,2'-spirobi[benzo[ ]stannole] ( ), is synthesised and the molecular structure is compared with the optimised geometry from DFT calculations. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are twice degenerated and show a small HOMO-LUMO energy gap of 3.2 eV. In addition, cyclic voltammetry measurements are conducted and three redox processes are observed. Absorption and emission spectra show maxima at λ 436 nm and λ 533 nm, respectively. Spirostannole is a strongly absorbing material, but an extremely weak emitter in solution at 295.15 K. However, when the solution is cooled from 280 to 80 K, the emission becomes visible. The reaction of spirostannole with methyllithium is monitored by NMR spectroscopy at 238.15 K. The Sn{ H} NMR signal shifts from -36.0 ( ) to -211.0 ppm, which is indicative of the formation of the lithium pentaorganostannate . The complex is thermally instable at 295.15 K, but insights into the molecular structure and electronic behaviour are obtained by DFT and TD-DFT calculations.