Introducing porous material into optical cavities is a critical step toward the utilization of quantum-electrodynamical (QED) effects for advanced technologies, e.g. in the context of sensing. We demonstrate that crystalline,...

Correction for ‘Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities’ by Ritesh Haldar et al., Chem. Sci., 2020, DOI: 10.1039/d0sc02436h.

The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine-C 60 dyads has been investigated. For this, two C 60-SiPc-C 60 dyads, 1 and 2, varying in their donor-acceptor distance, have been newly synthesized and characterized. In the case of C 60-SiPc-C 60 1 where the SiPc and C 60 are separated by a phenyl spacer, faster electron transfer was observed with k cs equal to 2.7 × 10 9 s À 1 in benzonitrile. However, in the case of C 60-SiPc-C 60 2, where SiPc and C 60 are separated by a biphenyl spacer, a slower electron transfer rate constant, k cs = 9.1 × 10 8 s À 1 , was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by~4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of~3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of 3 SiPc* as the end product and suggested the final lifetime of the charge separated state to be in the 3-20 ns range. Energy level diagrams established to comprehend these mechanistic details indicated that the comparatively highenergy SiPc * +-C 60 * À charge separated states (1.57 eV) populated the low-lying 3 SiPc* (1.26 eV) prior returning to the ground state.