Tuning Intramolecular Charge Transfer in Antimony(V) Porphyrin through Axial Fluorination

Modulation of intramolecular charge transfer (ICT) has been tested in two antimony(V) porphyrins, SbT(DMP)P(OMe)(2)<middle dot>PF6 and SbT(DMP)P(OTFE)(2)<middle dot>PF6, where the meso-positions are occupied by 3,5-dimethoxyphenyl (DMP), and the axial positions are linked with either methoxy (OMe) or trifluoroethoxy (OTFE) units, respectively. The presence of the Sb(+5) ion makes the porphyrin center electron poor. Under this situation, placing electron-rich units in the meso-position creates a condition for push-pull type ICT in the SbT(DMP)P(OMe)(2)<middle dot>PF6. Remarkably, it is shown that the ICT character can be further enhanced in SbT(DMP)P(OTFE)(2)<middle dot>PF6 with the help of electron-withdrawing TFE units in the axial position, which makes the porphyrin center even more electron scarce. The steady-state and transient studies as well as solvatochromism studies establish the ICT in SbT(DMP)P(OMe)(2)<middle dot>PF6 and SbT(DMP)P(OTFE)(2)<middle dot>PF6, and the strength of the ICT can be modulated by exploiting the structural properties of antimony(V) porphyrin. The existence of ICT is further supported by density functional theory calculations. The transient studies show that upon excitation of these porphyrin, their charge-transfer states convert to a full charger-separated states with appreciable lifetimes.