Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide

Anshuma Pathak; Achyut Bora; Björn Braunschweig; Christian Meltzer; Hongdan Yan; Peter Lemmens; Winfried Daum; Jeffrey Schwartz; Marc Tornow

doi:10.1039/c7nr02420g

Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide

Anshuma Pathak, Achyut Bora, Björn Braunschweig, Christian Meltzer, Hongdan Yan, Peter Lemmens, Winfried Daum, Jeffrey Schwartz, Marc Tornow

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-Al₂O₃ (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.

Original language	English (US)
Pages (from-to)	6291-6295
Number of pages	5
Journal	Nanoscale
Volume	9
Issue number	19
DOIs	https://doi.org/10.1039/c7nr02420g
State	Published - May 21 2017

All Science Journal Classification (ASJC) codes

General Materials Science

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title = "Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide",

abstract = "We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-Al2O3 (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.",

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T1 - Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide

AU - Pathak, Anshuma

AU - Bora, Achyut

AU - Braunschweig, Björn

AU - Meltzer, Christian

AU - Yan, Hongdan

AU - Lemmens, Peter

AU - Daum, Winfried

AU - Schwartz, Jeffrey

AU - Tornow, Marc

PY - 2017/5/21

Y1 - 2017/5/21

N2 - We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-Al2O3 (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.

AB - We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-Al2O3 (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.

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Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide

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