IR and Raman Vibrational Assignments for Metal-free Phthalocyanine from Density Functional B3LYP／6-31G（d） Method

Vibrational (IR and Raman) spectra for the metal-free phthalocyanine (H2Pc) have been comparatively investigated through experimental and theoretical methods. The frequencies and intensities were calculated at density functional B3LYP level using the 6-3 IG(d) basis set. The calculated vibrational frequencies were scaled by the factor 0.9613 and compared with the experimental result. In the IR spectrum, the characteristic IR band at 1008.cm^-1 is interpreted as C-N (pyrrole) in-plane bending vibration, in contrast with the traditional assigned N-H in-plane or out-of-plane bending vibration. The band at 874 cm^-1 is attributed to the isoindole deformation and aza vibration. In the Raman spectrum, the bands at 540, 566, 1310, 1340, 1425, 1448 and 1618 cm^-1 are also re-interpreted. Assignments of vibrational bands in the IR and Raman spectra are given based on density functional calculations for the first time. The present work provides valuable information to the traditional empirical assignment and will be helpful for further investigation of the vibration spectra of phthalocyanine analogues and their metal complexes.

IR and Raman Vibrational Assignments for Metal-free Phthalocyanine from Density Functional B3LYP/6-31G(d) Method

Vibrational (IR and Raman) spectra for the metal‐free phthalocyanine (H₂Pc) have been comparatively investigated through experimental and theoretical methods. The frequencies and intensities were calculated at density functional B3LYP level using the 6‐31G(d) basis set. The calculated vibrational frequencies were scaled by the factor 0.9613 and compared with the experimental result. In the IR spectrum, the characteristic IR band at 1008 cm^?1 is interpreted as C—N (pyrrole) in‐plane bending vibration, in contrast with the traditional assigned N—H in‐plane or out‐of‐plane bending vibration. The band at 874 cm^?1 is attributed to the isoindole deformation and aza vibration. In the Raman spectrum, the bands at 540. 566, 1310, 1340, 1425, 1448 and 1618 cm^?1 are also re‐interpreted. Assignments of vibrational bands in the IR and Raman spectra are given based on density functional calculations for the first time. The present work provides valuable information to the traditional empirical assignment and will be helpful for further investigation of the vibration spectra of phthalocyanine analogues and their metal complexes.