RESUMO
Bicyclo[1.1.1]pentane (BCP) motifs are of growing importance to the pharmaceutical industry as sp3 -rich bioisosteres of benzene rings and as molecular building blocks in materials science. Herein we explore the behavior of 1,3-disubstituted BCP moieties on metal surfaces by combining low-temperature scanning tunneling microscopy / non-contact atomic force microscopy studies with density functional theory modeling. We examine the configuration of individual BCP-containing precursors on Au(111), their supramolecular assembly and thermally activated dehalogenative coupling reactions, affording polymeric chains with incorporated electronically isolating units. Our studies not only provide the first sub-molecular insights of the BCP scaffold behavior on surfaces, but also extend the potential application of BCP derivatives towards integration in custom-designed surface architectures.
RESUMO
Linear modules equipped with two terminal hydroxamic acid groups act as the building block of diverse two-dimensional supramolecular motifs and patterns with room-temperature stability on the close-packed single-crystal surfaces of silver and gold, revealing a complex self-assembly scenario. By combining multiple investigation techniques (scanning tunneling microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations), we analyze the characteristics of the ordered assemblies which range from close-packed structures to polyporous networks featuring an exceptionally extended primitive unit cell with a side length exceeding 7â nm. The polyporous network shows potential for hosting and promoting the formation of chiral supramolecules, whereas a transition from 1D chiral randomness to an ordered racemate is discovered in a different porous phase. We correlate the observed structural changes to the adaptivity of the building block and surface-induced changes in the chemical state of the hydroxamic acid functional group.