ABSTRACT
A methoxy(alkenyl)carbenerhodium complex [RhCp*Cl{[double bond, length as m-dash]C(OMe)CH[double bond, length as m-dash]CPh2}(PMe3)]PF6 (2) has been synthesized and used as the starting material for the study of the effect of the metal center (Rh vs. Ir) in the formation of new rhodacycle complexes. While η3 and η5 indenylrhodium complexes have been achieved by the C-H bond activation of a phenyl ring, insertion of terminal alkynes into the rhodium-carbene bond led to the first example of the synthesis of rhodafuran complexes through rhoda-1,3,5-hexatriene intermediates. This new method represents an efficient process to obtain metallafuran complexes.
ABSTRACT
Chiroptical methods have been proven to be superior compared to their achiral counterparts for the structural elucidation of many compounds. To expand the use of chiroptical systems to everyday applications, the development of functional materials exhibiting intense chiroptical responses is essential. Particularly, tailored and robust interfaces compatible with standard device operation conditions are required. Herein, we present the design and synthesis of chiral allenes and their use for the functionalization of gold surfaces. The self-assembly results in a monolayer-thin room-temperature-stable upstanding chiral architecture as ascertained by ellipsometry, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure. Moreover, these nanostructures anchored to device-compatible substrates feature intense chiroptical second harmonic generation. Both straightforward preparation of the device-compatible interfaces along with their chiroptical nature provide major prospects for everyday applications.
