PMI–TDI Dyad
To enhance the bridge-mediated contributions to the electron coupling in the
electronic energy transfer process between the donor and the spacer in the dyad
system, we designed a dyad 21 in which a perylene monoimide (PMI) donor was
connected with a terrylene diimide (TDI) acceptor through a ladder-type
pentaphenylene (pPh) spacer [13]. The synthesis of the rigid ladder-type pPh spacer
19 is described elsewhere [14]. As discussed above, the facile synthesis of the
PMI-boronic ester 10 and the open form TDI boronic ester 13 made the route to the
target dyad 21 quite straightforward. As illustrated in Scheme 4, selective onefold
Suzuki coupling of spacer 19 with 10 afforded the PMI-pPh-Br 20, which was then
subjected to a further Suzuki coupling with 13. The precursor resulting from the
Suzuki coupling was further cyclized to give the target dyad 21.
PDI–TDI–PDI Triad
Besides the dyads, we also prepared the novel linear triad 27 (Scheme 5) with PDI
as donor and TDI as acceptor [15]. The synthesis of this acceptor–donor–acceptor
(A–D–A) multichromophore was accomplished by the Sonogashira coupling of an
asymmetric TDI 26 and a bifunctional PDI 24. To begin with, the bifunctionalized
dibromophenyl-PDI 22 was synthesized by imidization of PDA 4 and 4-bromo-2,6diisopropylaniline. After Suzuki coupling, halogenation and Sonogashira coupling,
Scheme 4 Synthesis of model dyad PMI-pPh-Ph-TDI 21
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T. Basche ´ et al.
To enhance the bridge-mediated contributions to the electron coupling in the
electronic energy transfer process between the donor and the spacer in the dyad
system, we designed a dyad 21 in which a perylene monoimide (PMI) donor was
connected with a terrylene diimide (TDI) acceptor through a ladder-type
pentaphenylene (pPh) spacer [13]. The synthesis of the rigid ladder-type pPh spacer
19 is described elsewhere [14]. As discussed above, the facile synthesis of the
PMI-boronic ester 10 and the open form TDI boronic ester 13 made the route to the
target dyad 21 quite straightforward. As illustrated in Scheme 4, selective onefold
Suzuki coupling of spacer 19 with 10 afforded the PMI-pPh-Br 20, which was then
subjected to a further Suzuki coupling with 13. The precursor resulting from the
Suzuki coupling was further cyclized to give the target dyad 21.
PDI–TDI–PDI Triad
Besides the dyads, we also prepared the novel linear triad 27 (Scheme 5) with PDI
as donor and TDI as acceptor [15]. The synthesis of this acceptor–donor–acceptor
(A–D–A) multichromophore was accomplished by the Sonogashira coupling of an
asymmetric TDI 26 and a bifunctional PDI 24. To begin with, the bifunctionalized
dibromophenyl-PDI 22 was synthesized by imidization of PDA 4 and 4-bromo-2,6diisopropylaniline. After Suzuki coupling, halogenation and Sonogashira coupling,
Scheme 4 Synthesis of model dyad PMI-pPh-Ph-TDI 21
70
T. Basche ´ et al.