π-Conjugation and Endgroup 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 ef- fects that influence their behavior. With support from Density Functional Theory (DFT) calculations, we have analyzed the IR and Raman spectra of cumulenes char- acterized by different endcapping groups and we have related it to the bond length alternation (BLA) pattern and local spectroscopic parameters associated to 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 endgroups. 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.