π‑Conjugation and End Group Effects in Long Cumulenes: Raman Spectroscopy and DFT Calculations

We have investigated the structure and spectroscopic properties of cumulenic carbon chains, focusing on the peculiar π-conjugation properties and end-group effects that influence their behavior. With support from Density Functional Theory (DFT) calculations, we have analyzed the IR and Raman spectra of cumulenes characterized by different end-capping groups and we have related them to the bond length alternation (BLA) pattern and local spectroscopic parameters associated with the CC bonds along the sp-carbon chain. For cumulenes we observe a breakdown of the correlation existing in polyynes among frequencies, Raman intensities of the R line (longitudinal CC stretching modes), and BLA. While the low R line frequency and equalized CC bonds would indicate the “metallic” character of cumulenic species, we obtain an unusually strong Raman intensity, which is typical of bond-alternated (semiconductive) structures. DFT calculations reveal that this is a consequence of π-electron conjugation, which markedly extends from the sp-carbon chain to the aryl rings belonging to the end groups. These findings suggest the existence of a strong electronic, vibrational and structural coupling between sp-carbon chains and sp²-carbon species, which could play a key role in nanostructured sp/sp²-hybrid carbon materials (e.g., linear carbon chains coupled to graphene domains). Within this context, Raman spectroscopy is a valuable tool for the detailed characterization of the molecular properties of this kind of materials