Layer-by-layer synthesis of metal-containing conducting polymers: caged metal centers for interlayer charge transport.
Metal-templated [2 + 3]-type cocondensation of a pi-extended boronic acid and nioxime furnished a series of cage molecules, which were electropolymerized to prepare metal-containing conducting polymers (MCPs). Despite sharing essentially isostructural organic scaffolds, these materials display metal-dependent electrochemical properties as evidenced by different redox windows observed for M = Co, Fe, Ru. Consecutive electropolymerization using two different monomers furnished bilayer MCPs having different metals in each layer. In addition to functioning as heavy atom markers in cross-sectional analysis by FIB and EDX, redox-active metal centers participate in voltage-dependent interlayer electron transport to give rise to cyclic voltammograms that are distinctively different from those of each layer alone or random copolymers. A simple electrochemical technique can thus be used as a straightforward diagnostic tool to investigate the structural ordering of electrically conductive layered materials.
Liu
Wenjun
W
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA.
Huang
Weijie
W
Pink
Maren
M
Lee
Dongwhan
D
D001897:Boronic Acids / Q000737:chemistry; D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D010091:Oximes / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*
D001897:Boronic Acids; D009942:Organometallic Compounds; D010091:Oximes; D011108:Polymers; D003035:Cobalt; D012428:Ruthenium; D007501:Iron