title: Insight into organometallic intermediate and its evolution to covalent bonding in surface-confined ullmann polymerization.
abstract: We provide insight into surface-catalyzed dehalogenative polymerization, analyzing the organometallic intermediate and its evolution into planar polymeric structures. A combined study using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and first-principles calculations unveils the structural conformation of substrate-bound phenylene intermediates generated from 1,4-dibromobenzene precursors on Cu(110), showing the stabilizing role of the halogen. The appearance of covalently bonded conjugated structures is followed in real time by fast-XPS measurements (with an acquisition time of 2 s per spectrum and heating rate of 2 K/s), showing that the detaching of phenylene units from the copper substrate and subsequent polymerization occur upon annealing above 460 ± 10 K.
authors.affiliation: Istituto di Struttura della Materia, CNR , Via Fosso del Cavaliere 100, 00133 Roma, Italy.
authors.forename: Marco
authors.initials: M
authors.lastname: Di Giovannantonio
authors.forename: Mohamed
authors.initials: M
authors.lastname: El Garah
authors.forename: Josh
authors.initials: J
authors.lastname: Lipton-Duffin
authors.forename: Vincent
authors.initials: V
authors.lastname: Meunier
authors.forename: Luis
authors.initials: L
authors.lastname: Cardenas
authors.forename: Yannick
authors.initials: Y
authors.lastname: Fagot Revurat
authors.forename: Albano
authors.initials: A
authors.lastname: Cossaro
authors.forename: Alberto
authors.initials: A
authors.lastname: Verdini
authors.forename: Dmitrii F
authors.initials: DF
authors.lastname: Perepichka
authors.forename: Federico
authors.initials: F
authors.lastname: Rosei
authors.forename: Giorgio
authors.initials: G
authors.lastname: Contini