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Nature Research, Nature Communications, 1(12), 2021

DOI: 10.1038/s41467-021-26385-7

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

Journal article published in 2021 by Ibrahim Deneme ORCID, Gorkem Liman, Ayse Can, Gokhan Demirel ORCID, Hakan Usta ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

AbstractMolecular engineering via functionalization has been a great tool to tune noncovalent intermolecular interactions. Herein, we demonstrate three-dimensional highly crystalline nanostructured D(C7CO)-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.