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Patrício S, Cruz AI, Biernacki K, et al. Novel layer-by-layer interfacial [Ni(salen)]-polyelectrolyte hybrid films. Langmuir. 2010;26(13):10842-53doi: 10.1021/la1006956.
Patrício, S., Cruz, A. I., Biernacki, K., Ventura, J., Eaton, P., Magalhães, A. L., Moura, C., Hillman, A. R., & Freire, C. (2010). Novel layer-by-layer interfacial [Ni(salen)]-polyelectrolyte hybrid films. Langmuir : the ACS journal of surfaces and colloids, 26(13), 10842-53. https://doi.org/10.1021/la1006956
Patrício, Sónia, et al. "Novel layer-by-layer interfacial [Ni(salen)]-polyelectrolyte hybrid films." Langmuir : the ACS journal of surfaces and colloids vol. 26,13 (2010): 10842-53. doi: https://doi.org/10.1021/la1006956
Patrício S, Cruz AI, Biernacki K, Ventura J, Eaton P, Magalhães AL, Moura C, Hillman AR, Freire C. Novel layer-by-layer interfacial [Ni(salen)]-polyelectrolyte hybrid films. Langmuir. 2010 Jul 06;26(13):10842-53. doi: 10.1021/la1006956. PMID: 20476725.
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Langmuir. 2010 Jul 06;26(13):10842-53. doi: 10.1021/la1006956.

Novel layer-by-layer interfacial [Ni(salen)]-polyelectrolyte hybrid films.

Langmuir : the ACS journal of surfaces and colloids

Sónia Patrício, Ana I Cruz, Krzysztof Biernacki, João Ventura, Peter Eaton, Alexandre L Magalhães, Cosme Moura, A Robert Hillman, Cristina Freire

Affiliations

  1. REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal.

PMID: 20476725 DOI: 10.1021/la1006956

Abstract

A novel multilayer film containing a cationic phosphonium-derivatized Ni(salen)-type complex and poly(sodium-4-styrenesulfonate (NaPSS) was assembled onto quartz, mica, and metal surfaces using the layer-by-layer (LbL) technique. Spectroscopic (UV-vis) and gravimetric (QCM) responses for the multilayer films show regular stepwise growth and the signature of strong electrostatic interactions between the component layers. The gravimetric responses indicate the presence of substantial additional (net neutral) material in the PSS layers, which XPS shows is not polyelectrolyte or salt, so charge compensation is intrinsic; we deduce the presence of space-filling solvent. Direct electrostatic interaction of the two-component layers is enhanced by a secondary noncovalent interaction between the delocalized pi-systems of the two components. Permeability of the film to the redox probe [Fe(CN)(6)](3-/4-) was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Qualitatively similar results were obtained in the absence and presence of a precursor PSS/PAH multilayer, but with a general shift in kinetic and diffusional processes to longer time scales (lower frequencies) in the presence of the precursor layer and with increasing numbers of PSS/[Ni(salen)] bilayers. Quantitatively, the EIS data were interpreted using a capillary membrane model (CMM) to yield values of coverage, apparent charge transfer resistance, double-layer capacitance, pore size, and diffusion coefficient. The coverage values were consistent with a model in which there are no preferential growth sites and the surface charge density is independent of the number of bilayers.

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