A fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films

Self-assembled polyelectrolyte multilayer films comprised of poly(allylamine) derivatized with an Os-(bpy)2CIPyCH- complex (PAH-Os), and poly(vinylsulfonate), PVS, or poly(styrensulfonate), PSS, have been studied by Fourier transform infrared reflection-absorption spectroscopy. The infrared absorban...

Descripción completa

Guardado en:
Detalles Bibliográficos
Autores principales: Bonazzola, C., Calvo, E.J., Nart, F.C.
Formato: JOUR
Materias:
Absorption
Electrostatics
Fourier transform infrared spectroscopy
Molecular vibrations
Multilayers
Osmium compounds
Oxidation
Redox reactions
Self assembly
Polyallylamine
Polyelectolyte multilayer films
Polystyrensulfonate
Polyvinylsulfonate
Redox charge
Polyelectrolytes
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_07437463_v19_n13_p5279_Bonazzola
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_07437463_v19_n13_p5279_Bonazzola
record_format dspace
spelling todo:paper_07437463_v19_n13_p5279_Bonazzola2023-10-03T15:38:35Z A fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films Bonazzola, C. Calvo, E.J. Nart, F.C. Absorption Electrostatics Fourier transform infrared spectroscopy Molecular vibrations Multilayers Osmium compounds Oxidation Redox reactions Self assembly Polyallylamine Polyelectolyte multilayer films Polystyrensulfonate Polyvinylsulfonate Redox charge Polyelectrolytes Self-assembled polyelectrolyte multilayer films comprised of poly(allylamine) derivatized with an Os-(bpy)2CIPyCH- complex (PAH-Os), and poly(vinylsulfonate), PVS, or poly(styrensulfonate), PSS, have been studied by Fourier transform infrared reflection-absorption spectroscopy. The infrared absorbances of the characteristic SO3-, CH2, NH3+, and aromatic bipyridine and pyridine groups have been characterized, and their intensity increases with the number of self-assembled layers and redox charge. The characteristic infrared signatures are the 1040 cm-1 band assigned to the aromatic ligands in the osmium complex (v(Py)), PAH-Os, and the 1040 cm-1 (vs(SO3-)) and 1213 cm-1 (va(SO3-)) bands for SO3 groups in PVS. The vs(SO3-) vibrational mode of PVS senses the local NH3+ environment of the cationic PAH-Os resulting in a band shift of 22 cm-1 for the first polyallylamine layer. Subtractively normalized Fourier transform infrared spectroscopy during the oxidation of the Os centers in the (PAH-Os)n(PVS)m multilayer reveals that different vibrational modes of bipyridine ligands in the osmium redox center of PAH-Os and the sulfonate groups of PVS are affected by charge-ligand electrostatic interaction and dipole reorganization in the multilayers. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_07437463_v19_n13_p5279_Bonazzola
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Absorption
Electrostatics
Fourier transform infrared spectroscopy
Molecular vibrations
Multilayers
Osmium compounds
Oxidation
Redox reactions
Self assembly
Polyallylamine
Polyelectolyte multilayer films
Polystyrensulfonate
Polyvinylsulfonate
Redox charge
Polyelectrolytes
spellingShingle Absorption
Electrostatics
Fourier transform infrared spectroscopy
Molecular vibrations
Multilayers
Osmium compounds
Oxidation
Redox reactions
Self assembly
Polyallylamine
Polyelectolyte multilayer films
Polystyrensulfonate
Polyvinylsulfonate
Redox charge
Polyelectrolytes
Bonazzola, C.
Calvo, E.J.
Nart, F.C.
A fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films
topic_facet Absorption
Electrostatics
Fourier transform infrared spectroscopy
Molecular vibrations
Multilayers
Osmium compounds
Oxidation
Redox reactions
Self assembly
Polyallylamine
Polyelectolyte multilayer films
Polystyrensulfonate
Polyvinylsulfonate
Redox charge
Polyelectrolytes
description Self-assembled polyelectrolyte multilayer films comprised of poly(allylamine) derivatized with an Os-(bpy)2CIPyCH- complex (PAH-Os), and poly(vinylsulfonate), PVS, or poly(styrensulfonate), PSS, have been studied by Fourier transform infrared reflection-absorption spectroscopy. The infrared absorbances of the characteristic SO3-, CH2, NH3+, and aromatic bipyridine and pyridine groups have been characterized, and their intensity increases with the number of self-assembled layers and redox charge. The characteristic infrared signatures are the 1040 cm-1 band assigned to the aromatic ligands in the osmium complex (v(Py)), PAH-Os, and the 1040 cm-1 (vs(SO3-)) and 1213 cm-1 (va(SO3-)) bands for SO3 groups in PVS. The vs(SO3-) vibrational mode of PVS senses the local NH3+ environment of the cationic PAH-Os resulting in a band shift of 22 cm-1 for the first polyallylamine layer. Subtractively normalized Fourier transform infrared spectroscopy during the oxidation of the Os centers in the (PAH-Os)n(PVS)m multilayer reveals that different vibrational modes of bipyridine ligands in the osmium redox center of PAH-Os and the sulfonate groups of PVS are affected by charge-ligand electrostatic interaction and dipole reorganization in the multilayers.
format JOUR
author Bonazzola, C.
Calvo, E.J.
Nart, F.C.
author_facet Bonazzola, C.
Calvo, E.J.
Nart, F.C.
author_sort Bonazzola, C.
title A fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films
title_short A fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films
title_full A fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films
title_fullStr A fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films
title_full_unstemmed A fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films
title_sort fourier transform infrared reflection-absorption spectroscopy study of redox polyelectrolyte films
url http://hdl.handle.net/20.500.12110/paper_07437463_v19_n13_p5279_Bonazzola
work_keys_str_mv AT bonazzolac afouriertransforminfraredreflectionabsorptionspectroscopystudyofredoxpolyelectrolytefilms
AT calvoej afouriertransforminfraredreflectionabsorptionspectroscopystudyofredoxpolyelectrolytefilms
AT nartfc afouriertransforminfraredreflectionabsorptionspectroscopystudyofredoxpolyelectrolytefilms
AT bonazzolac fouriertransforminfraredreflectionabsorptionspectroscopystudyofredoxpolyelectrolytefilms
AT calvoej fouriertransforminfraredreflectionabsorptionspectroscopystudyofredoxpolyelectrolytefilms
AT nartfc fouriertransforminfraredreflectionabsorptionspectroscopystudyofredoxpolyelectrolytefilms
_version_ 1782027042290663424

Ejemplares similares