Self-assembled monolayers of disulfide Cu porphyrins on au surfaces: Adsorption induced reduction and demetalation
Metalloporphyrin molecules have a wide range of potential applications in diverse technological areas ranging from electronics to optoelectronics, electrochemistry, photophysics, chemical sensors, and catalysis. In particular, self-assembled monolayers of porphyrin molecules have recently attracted...
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2011
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paper:paper_07437463_v27_n17_p10714_VeronicaRivas2023-06-08T15:44:59Z Self-assembled monolayers of disulfide Cu porphyrins on au surfaces: Adsorption induced reduction and demetalation Au surfaces Demetalation Electrochemical techniques Functionalized Metal centers Metalloporphyrin molecules Molecular aggregate Packed arrays Photophysics Polarization modulation infrared reflection absorption spectroscopy Porphyrin molecules Porphyrin rings Potential applications Surface normals UV-Vis absorption spectroscopy Absorption Absorption spectroscopy Adsorption Electrochemistry Functional groups Molecules Photoelectron spectroscopy Porphyrins Reduction Self assembly Ultraviolet spectroscopy Self assembled monolayers copper disulfide gold metalloporphyrin adsorption article artificial membrane chemical structure chemistry oxidation reduction reaction surface property Adsorption Copper Disulfides Gold Membranes, Artificial Metalloporphyrins Molecular Structure Oxidation-Reduction Surface Properties Metalloporphyrin molecules have a wide range of potential applications in diverse technological areas ranging from electronics to optoelectronics, electrochemistry, photophysics, chemical sensors, and catalysis. In particular, self-assembled monolayers of porphyrin molecules have recently attracted considerable interest. In this work we have studied for the first time the self-assembly of a novel Cu deutero porphyrin functionalized with disulfide moieties using electrochemical techniques, UV-vis absorption spectroscopy, polarization modulation infrared reflection absorption spectroscopy, and photoelectron spectroscopies (XPS and UPS). Experimental results indicate that the molecule adsorbs retaining its molecular integrity without forming molecular aggregates via the formation of Au-S covalent bonds. Furthermore, the monolayer consists of a packed array of molecules adsorbed with the plane of the porphyrin molecule at an angle of around 30° with respect to the surface normal. Interestingly, adsorption induces reduction of the Cu center and its consequent removal from the center of the porphyrin ring resulting in porphyrin demetalation. Our results are important in the design of self-assembled monolayers of metallo porphyrins where not only blocking of the metal center by the functional groups that drive the self-assembly should be considered but also possible adsorption induced demetalation with the consequent loss in the properties imparted by the metal center. © 2011 American Chemical Society. 2011 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07437463_v27_n17_p10714_VeronicaRivas http://hdl.handle.net/20.500.12110/paper_07437463_v27_n17_p10714_VeronicaRivas |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Au surfaces Demetalation Electrochemical techniques Functionalized Metal centers Metalloporphyrin molecules Molecular aggregate Packed arrays Photophysics Polarization modulation infrared reflection absorption spectroscopy Porphyrin molecules Porphyrin rings Potential applications Surface normals UV-Vis absorption spectroscopy Absorption Absorption spectroscopy Adsorption Electrochemistry Functional groups Molecules Photoelectron spectroscopy Porphyrins Reduction Self assembly Ultraviolet spectroscopy Self assembled monolayers copper disulfide gold metalloporphyrin adsorption article artificial membrane chemical structure chemistry oxidation reduction reaction surface property Adsorption Copper Disulfides Gold Membranes, Artificial Metalloporphyrins Molecular Structure Oxidation-Reduction Surface Properties |
| spellingShingle |
Au surfaces Demetalation Electrochemical techniques Functionalized Metal centers Metalloporphyrin molecules Molecular aggregate Packed arrays Photophysics Polarization modulation infrared reflection absorption spectroscopy Porphyrin molecules Porphyrin rings Potential applications Surface normals UV-Vis absorption spectroscopy Absorption Absorption spectroscopy Adsorption Electrochemistry Functional groups Molecules Photoelectron spectroscopy Porphyrins Reduction Self assembly Ultraviolet spectroscopy Self assembled monolayers copper disulfide gold metalloporphyrin adsorption article artificial membrane chemical structure chemistry oxidation reduction reaction surface property Adsorption Copper Disulfides Gold Membranes, Artificial Metalloporphyrins Molecular Structure Oxidation-Reduction Surface Properties Self-assembled monolayers of disulfide Cu porphyrins on au surfaces: Adsorption induced reduction and demetalation |
| topic_facet |
Au surfaces Demetalation Electrochemical techniques Functionalized Metal centers Metalloporphyrin molecules Molecular aggregate Packed arrays Photophysics Polarization modulation infrared reflection absorption spectroscopy Porphyrin molecules Porphyrin rings Potential applications Surface normals UV-Vis absorption spectroscopy Absorption Absorption spectroscopy Adsorption Electrochemistry Functional groups Molecules Photoelectron spectroscopy Porphyrins Reduction Self assembly Ultraviolet spectroscopy Self assembled monolayers copper disulfide gold metalloporphyrin adsorption article artificial membrane chemical structure chemistry oxidation reduction reaction surface property Adsorption Copper Disulfides Gold Membranes, Artificial Metalloporphyrins Molecular Structure Oxidation-Reduction Surface Properties |
| description |
Metalloporphyrin molecules have a wide range of potential applications in diverse technological areas ranging from electronics to optoelectronics, electrochemistry, photophysics, chemical sensors, and catalysis. In particular, self-assembled monolayers of porphyrin molecules have recently attracted considerable interest. In this work we have studied for the first time the self-assembly of a novel Cu deutero porphyrin functionalized with disulfide moieties using electrochemical techniques, UV-vis absorption spectroscopy, polarization modulation infrared reflection absorption spectroscopy, and photoelectron spectroscopies (XPS and UPS). Experimental results indicate that the molecule adsorbs retaining its molecular integrity without forming molecular aggregates via the formation of Au-S covalent bonds. Furthermore, the monolayer consists of a packed array of molecules adsorbed with the plane of the porphyrin molecule at an angle of around 30° with respect to the surface normal. Interestingly, adsorption induces reduction of the Cu center and its consequent removal from the center of the porphyrin ring resulting in porphyrin demetalation. Our results are important in the design of self-assembled monolayers of metallo porphyrins where not only blocking of the metal center by the functional groups that drive the self-assembly should be considered but also possible adsorption induced demetalation with the consequent loss in the properties imparted by the metal center. © 2011 American Chemical Society. |
| title |
Self-assembled monolayers of disulfide Cu porphyrins on au surfaces: Adsorption induced reduction and demetalation |
| title_short |
Self-assembled monolayers of disulfide Cu porphyrins on au surfaces: Adsorption induced reduction and demetalation |
| title_full |
Self-assembled monolayers of disulfide Cu porphyrins on au surfaces: Adsorption induced reduction and demetalation |
| title_fullStr |
Self-assembled monolayers of disulfide Cu porphyrins on au surfaces: Adsorption induced reduction and demetalation |
| title_full_unstemmed |
Self-assembled monolayers of disulfide Cu porphyrins on au surfaces: Adsorption induced reduction and demetalation |
| title_sort |
self-assembled monolayers of disulfide cu porphyrins on au surfaces: adsorption induced reduction and demetalation |
| publishDate |
2011 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07437463_v27_n17_p10714_VeronicaRivas http://hdl.handle.net/20.500.12110/paper_07437463_v27_n17_p10714_VeronicaRivas |
| _version_ |
1768544554918608896 |