Cargando…

Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms

Molecular engineering via functionalization has been a great tool to tune noncovalent intermolecular interactions. Herein, we demonstrate three-dimensional highly crystalline nanostructured D(C(7)CO)-BTBT films via carbonyl-functionalization of a fused thienoacene π-system, and strong Raman signal e...

Descripción completa

Detalles Bibliográficos
Autores principales: Deneme, Ibrahim, Liman, Gorkem, Can, Ayse, Demirel, Gokhan, Usta, Hakan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8531383/
https://www.ncbi.nlm.nih.gov/pubmed/34675208
http://dx.doi.org/10.1038/s41467-021-26385-7
_version_ 1784586844586901504
author Deneme, Ibrahim
Liman, Gorkem
Can, Ayse
Demirel, Gokhan
Usta, Hakan
author_facet Deneme, Ibrahim
Liman, Gorkem
Can, Ayse
Demirel, Gokhan
Usta, Hakan
author_sort Deneme, Ibrahim
collection PubMed
description Molecular engineering via functionalization has been a great tool to tune noncovalent intermolecular interactions. Herein, we demonstrate three-dimensional highly crystalline nanostructured D(C(7)CO)-BTBT films via carbonyl-functionalization of a fused thienoacene π-system, and strong Raman signal enhancements in Surface-Enhanced Raman Spectroscopy (SERS) are realized. The small molecule could be prepared on the gram scale with a facile synthesis-purification. In the engineered films, polar functionalization induces favorable out-of-plane crystal growth via zigzag motif of dipolar C = O···C = O interactions and hydrogen bonds, and strengthens π-interactions. A unique two-stage film growth behavior is identified with an edge-on-to-face-on molecular orientation transition driven by hydrophobicity. The analysis of the electronic structures and the ratio of the anti-Stokes/Stokes SERS signals suggests that the π-extended/stabilized LUMOs with varied crystalline face-on orientations provide the key properties in the chemical enhancement mechanism. A molecule-specific Raman signal enhancement is also demonstrated on a high-LUMO organic platform. Our results demonstrate a promising guidance towards realizing low-cost SERS-active semiconducting materials, increasing structural versatility of organic-SERS platforms, and advancing molecule-specific sensing via molecular engineering.
format Online
Article
Text
id pubmed-8531383
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher Nature Publishing Group UK
record_format MEDLINE/PubMed
spelling pubmed-85313832021-11-15 Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms Deneme, Ibrahim Liman, Gorkem Can, Ayse Demirel, Gokhan Usta, Hakan Nat Commun Article Molecular engineering via functionalization has been a great tool to tune noncovalent intermolecular interactions. Herein, we demonstrate three-dimensional highly crystalline nanostructured D(C(7)CO)-BTBT films via carbonyl-functionalization of a fused thienoacene π-system, and strong Raman signal enhancements in Surface-Enhanced Raman Spectroscopy (SERS) are realized. The small molecule could be prepared on the gram scale with a facile synthesis-purification. In the engineered films, polar functionalization induces favorable out-of-plane crystal growth via zigzag motif of dipolar C = O···C = O interactions and hydrogen bonds, and strengthens π-interactions. A unique two-stage film growth behavior is identified with an edge-on-to-face-on molecular orientation transition driven by hydrophobicity. The analysis of the electronic structures and the ratio of the anti-Stokes/Stokes SERS signals suggests that the π-extended/stabilized LUMOs with varied crystalline face-on orientations provide the key properties in the chemical enhancement mechanism. A molecule-specific Raman signal enhancement is also demonstrated on a high-LUMO organic platform. Our results demonstrate a promising guidance towards realizing low-cost SERS-active semiconducting materials, increasing structural versatility of organic-SERS platforms, and advancing molecule-specific sensing via molecular engineering. Nature Publishing Group UK 2021-10-21 /pmc/articles/PMC8531383/ /pubmed/34675208 http://dx.doi.org/10.1038/s41467-021-26385-7 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Deneme, Ibrahim
Liman, Gorkem
Can, Ayse
Demirel, Gokhan
Usta, Hakan
Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms
title Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms
title_full Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms
title_fullStr Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms
title_full_unstemmed Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms
title_short Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms
title_sort enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-sers platforms
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8531383/
https://www.ncbi.nlm.nih.gov/pubmed/34675208
http://dx.doi.org/10.1038/s41467-021-26385-7
work_keys_str_mv AT denemeibrahim enablingthreedimensionalporousarchitecturesviacarbonylfunctionalizationandmolecularspecificorganicsersplatforms
AT limangorkem enablingthreedimensionalporousarchitecturesviacarbonylfunctionalizationandmolecularspecificorganicsersplatforms
AT canayse enablingthreedimensionalporousarchitecturesviacarbonylfunctionalizationandmolecularspecificorganicsersplatforms
AT demirelgokhan enablingthreedimensionalporousarchitecturesviacarbonylfunctionalizationandmolecularspecificorganicsersplatforms
AT ustahakan enablingthreedimensionalporousarchitecturesviacarbonylfunctionalizationandmolecularspecificorganicsersplatforms