Hydrogen Bond-Mediated Conjugates Involving Lanthanide Diphthalocyanines and Trifluoroacetic Acid (Lnpc₂@TFA):...

The interaction between lanthanide diphthalocyanine complexes, LnPc₂ (Ln = Nd, Sm, Eu, Gd, Yb, Lu; Pc = C₃₂H₁₆N₈, phthalocyanine ligand) and trifluoroacetic acid (TFA) was investigated in benzene, and the stability of the resulting molecular system was assessed based on spectral (UV-Vis) and kinetic measurements. Structural Density Functional Theory (DFT) calculations provided interesting data regarding the nature of the bonding and allowed estimating the interaction energy between the LnPc₂ and TFA species. Conjugates are created between the LnPc₂ and TFA molecules via hydrogen bonds of moderate strength (>N∙∙H··) at the meso- -bridges of the Pc moieties, which renders the sandwich system to flatten. Attachment of TFA is followed by rearrangement of electronic density within the chromophore system of the macrocycles manifested in considerable changes in their UV-Vis spectra and consequently the color of the studied solutions (from green to orange). The LnPc₂@TFA conjugates including Nd, Sm, Eu, and Gd appeared evidently less photostable when exposed to UV radiation than the related mother compounds, whereas in the case of Yb and Lu derivatives some TFA-prompted stabilizing effect was noticed. The conjugates displayed the capacity for singlet oxygen generation in contrast to the LnPc₂s itself. Photon upconversion through sensitized triplet-triplet annihilation was demonstrated by the TFA conjugates of Nd, Sm, Eu, and Gd.