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Macrocyclic Dyads Based on C 60 and Perylenediimides Connected by Click Chemistry
Author(s) -
Pla Sara,
MartínGomis Luis,
Ohkubo Kei,
Fukuzumi Shunichi,
FernándezLázaro Fernando,
SastreSantos Ángela
Publication year - 2014
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201300235
Subject(s) - chemistry , triad (sociology) , intersystem crossing , ultrafast laser spectroscopy , photochemistry , flash photolysis , fullerene , absorption (acoustics) , electron transfer , rotaxane , click chemistry , piperidine , acceptor , supramolecular chemistry , reaction rate constant , polymer chemistry , stereochemistry , molecule , excited state , laser , kinetics , organic chemistry , psychoanalysis , acoustics , optics , condensed matter physics , psychology , quantum mechanics , nuclear physics , physics , singlet state
Two sets of perylenediimide‐[60]fullerene dyads PDI‐C 60 connected through 1,2,3‐triazole units have been synthesized and characterized. The cyclic dyad PDICl 4 ‐C 60 has four chlorine atoms in the 1,6,7,12‐PDI positions, whereas the cyclic dyad PDIPip 2 ‐C 60 has two piperidine units in the 1,7‐PDI positions. On the other hand, PDICl 4 ‐C 60 and PDIPip 2 ‐C 60 dyads were synthesized as linear counterparts with the same substitution pattern. Also, a C 60 ‐PDICl 4 ‐C 60 triad has been prepared. A small interaction between C 60 and PDI moieties in the ground state was detected by UV/vis and electrochemical measurements in both PDI‐C 60 cyclic systems. The occurrence of photoinduced energy‐transfer processes between PDI and C 60 units was confirmed by time‐resolved emission and transient absorption techniques. Femtosecond laser flash photolysis showed energy transfer from 1 PDI* to C 60 followed by intersystem crossing from 1 C 60 * to 3 C 60 * in the case of the PDICl 4 ‐C 60 systems. The energy transfer rate for PDICl 4 ‐C 60 in the cyclic dyad and the triad is one order of magnitude faster than that in PDICl 4 ‐C 60 in the linear dyad. The fast energy transfer rate together with the enhanced molar absorption coefficient by perylenediimide functionalization will be highly beneficial for applications as acceptors in polymer solar cells. On the other hand, no electron transfer from the donor PDIpip 2 units to the acceptor C 60 moiety was detected in the case of PDIPip 2 ‐C 60 dyads.