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Advances in Supramolecular Chemistry, Volume 4 (Advances in by G.W. Gokel

By G.W. Gokel

A part of a sequence which provides studies of efforts in all components of supramolecular technological know-how, this quantity discusses a number of issues within the box.

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In contrast to Figure 1, the direction of the electron transfer is such that the process is encouraged only when the cationic guest is bound to the receptor. Now luminescence loses the competition when cationic guests are present on/in the receptor. (b) Frontier molecular orbital diagrams corresponding to part (a). The intermolecular electron transfer is exergonic only in the cation-bound case when the LUMO' of the receptor is lower in energy than the LUMO of the lumophore. Note that the LUMO' and the HOMO' of the receptor are stabilized upon cation binding.

Continued) Co) (i) LUMO -- LUMO" e" I HOMO f / 41 4I 1~ _ HOMO' (ii) LUMO tlOMO" - LUMO" hvL,,,. oMo, (iii)LUMO HOMO HOMO" LUMO" 1 HOMO' ~ HOMO" Cc) •L• 88 NH2 long wave luminescence 'on' short wave luminescence 'off' (ii) o // '~t 89 short wave luminc~encr 'on' H2 long wave luminescence 'on' Figure 12. (continued) (b) Frontier molecular orbital energy diagrams corresponding to part (a). Note that in situation (i) the energies of HOMO, HOMO', and HOMO" are similar, whereas LUMO" lies lower in energy than LUMO.

Besides its utility for biomonitoring, 88 also shows how the competition between PET and EET is influenced by pH. In particular, 88 acts as a triad system. Some triads have received much attention as solar energy converters. 92 EET in 88 occurs across an intervening electron pair via a "stepping stone" mechanism. Interestingly, this stepping stone can be ionically switched in or out of the EET path. 42 As mentioned in Section 4, multi-lumophore versions of lumophore-spacer-receptor systems can also produce a pair of spectral observables (monomer and excimer emission) which can be employed for purposes of internally referenced sensing/switching.

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