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

Creative Commons License

Deneme I., Liman G., Can A., Demirel G., Usta H.

NATURE COMMUNICATIONS, cilt.12, ss.1-6, 2021 (SCI-Expanded) identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 12
  • Basım Tarihi: 2021
  • Doi Numarası: 10.1038/s41467-021-26385-7
  • Dergi Adı: NATURE COMMUNICATIONS
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, BIOSIS, CAB Abstracts, Chemical Abstracts Core, EMBASE, Geobase, INSPEC, MEDLINE, Veterinary Science Database, Directory of Open Access Journals
  • Sayfa Sayıları: ss.1-6
  • Gazi Üniversitesi Adresli: Evet

Özet

Molecular 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.