Molecular-Enhanced Raman Spectroscopy Driven by Phosphoester Electron-Transfer Bridge.

Although both electromagnetic and charge transfer (CT) mechanisms play a role in surface-enhanced Raman scattering (SERS), the contribution of the latter is limited by poor CT efficiency. Herein, we propose molecular-enhanced Raman spectroscopy (MERS) for the first time and develop a simple strategy to induce strong CT-enhanced Raman signals using a phosphoester (POE) electron-transfer bridge. Consequently, an excellent POE-enhanced Raman effect was found when various mono-, bis-, and trisaminobenzene compounds were used as probe analytes. Quantification analysis of this MERS effect revealed that the enhancement ratio and factor of the POE molecules can be up to 87% and ∼10, respectively. Spectroscopic analysis and density functional theory calculation confirmed that this effect was because of the formation of intermolecular hydrogen bonds, which promotes CT via electronic reorganization and enhances the Raman signals of target analytes. These results demonstrate the feasibility of MERS for highly CT-enhanced Raman signals.