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To quantify the differences between the rates of charge separation (kCS) and charge recombination (kCR, we performed a simultaneous target analysis of compounds oc and oc2. The kinetic model used consists of a biexponential decay of the excited state to a charge-separated state, which in turn decays with kCR. In order to limit the number of free parameters, the SADS of the excited state were assumed to be identical in oc and oc2, as well as the fractions of slow and fast charge separation (see also ref 23, For the charge-separated state, both the SADS and the &CR were assumed to be identical in oc and oc2. Thus, the difference between oc and oc2 is quantified by the rates of slow (the dominant fraction) and fast charge separation the minor fraction; see ref 23
-
CR. In order to limit the number of free parameters, the SADS of the excited state were assumed to be identical in oc and oc2, as well as the fractions of slow and fast charge separation (see also ref 23). For the charge-separated state, both the SADS and the &CR were assumed to be identical in oc and oc2. Thus, the difference between oc and oc2 is quantified by the rates of slow (the dominant fraction) and fast charge separation (the minor fraction; see ref 23).
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A second minor deactivation pathway with 20% amplitude of the singlet excited state of compound oc is observed in toluene which is most probably related to the decay of a second possible pinched-cone conformation of the calix[4]arene moiety. As we are dealing here with merely conformational isomers, the additionally assumed species of this second pathway has identical spectral features and an indistinguishable depopulation pathway to the ground state.
-
A second minor deactivation pathway with 20% amplitude of the singlet excited state of compound oc is observed in toluene which is most probably related to the decay of a second possible pinched-cone conformation of the calix[4]arene moiety. As we are dealing here with merely conformational isomers, the additionally assumed species of this second pathway has identical spectral features and an indistinguishable depopulation pathway to the ground state.
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As discussed before (see ref 23, faster components are also observed for the data of compound oc in the solvents CH2Cl2 (7.7 ps, 32, and benzonitrile (8.3 ps, 33, These are again attributable to the second pinched-cone conformation of the calix[4]arene moiety. Likewise, for compound oc2 in all three solvents, a fast component showing a lifetime of < 1 ps (20, in toluene, 3.6 ps (32, in CH2C2, and 3.8 ps 33, in benzonitrile is observed. Note that, again, the lifetimes of this faster component of compound oc2 reduce by half compared with those obtained for compound oc for the respective solvents owing to the availability of a second electron-transfer deactivation channel in compound oc2
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2, and 3.8 ps (33%) in benzonitrile is observed. Note that, again, the lifetimes of this faster component of compound oc2 reduce by half compared with those obtained for compound oc for the respective solvents owing to the availability of a second electron-transfer deactivation channel in compound oc2.
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