PMID- 17020252
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20070913
LR  - 20061005
IS  - 1089-5639 (Print)
IS  - 1089-5639 (Linking)
VI  - 110
IP  - 40
DP  - 2006 Oct 12
TI  - Synthesis and photophysical investigation of new porphyrin derivatives with 
      beta-pyrrole ethynyl linkage and corresponding dyad with [60] fullerene.
PG  - 11424-34
AB  - Two new beta-substituted arylethynyl meso-tetraphenylporphyrins, 
      2-[(4'-formyl)phenyl]ethynyl-5,10,15,20-tetraphenylporphyrin (system A) and 
      2-[(4'-methyl)phenyl]ethynyl-5,10,15,20-tetraphenylporphyrin (system B) and their 
      zinc derivatives were synthesized by palladium catalysis, using a synthetic 
      approach that affords high yields of the target systems. Comparative 
      ultraviolet-visible (UV-vis), NMR, and cyclic voltammetry studies of such 
      macrocycles reveal the presence of an extensive conjugation between the 
      tetrapyrrolic ring and the linker, through pi-pi orbital interaction. This 
      interaction was observed in the form of a "push-pull" effect that moves the 
      electronic charge between the porphyrin and the aldehyde group of system A. 
      System B, bearing a methyl group instead of the formyl group, was synthesized in 
      order to evaluate the effect of the substitution on the charge delocalization, 
      which is necessary to corroborate the push-pull mechanism hypothesis. The new 
      porphyrin, system A, was also used as a starting material for the synthesis of 
      new porphyrin-fullerene dyads in which the [60]fullerene is directly linked to 
      the tetrapyrrolic rings by ethynylenephenylene subunits. Fluorescence and 
      transient absorption measurements of the new dyads reveal that ultrafast energy 
      and electron transfer occur, respectively, in nonpolar and polar solvents, with 
      high values of the rate constant. The UV-vis, NMR, and cyclic voltammetry results 
      show that it is possible for both energy and electron transfer between porphyrin 
      and fullerene to take place through the pi-bond interaction. Such results 
      evidence that the coupling between the donor and acceptor moieties is strong 
      enough for possible photovoltaic applications.
FAU - Lembo, Angelo
AU  - Lembo A
AD  - Institute for Physical Chemistry, Friedrich-Alexander University 
      Erlangen-Nurberg, Egerlandstrasse 3, 91058 Erlangen, Germany.
FAU - Tagliatesta, Pietro
AU  - Tagliatesta P
FAU - Guldi, Dirk M
AU  - Guldi DM
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Phys Chem A
JT  - The journal of physical chemistry. A
JID - 9890903
EDAT- 2006/10/06 09:00
MHDA- 2006/10/06 09:01
CRDT- 2006/10/06 09:00
PHST- 2006/10/06 09:00 [pubmed]
PHST- 2006/10/06 09:01 [medline]
PHST- 2006/10/06 09:00 [entrez]
AID - 10.1021/jp062735h [doi]
PST - ppublish
SO  - J Phys Chem A. 2006 Oct 12;110(40):11424-34. doi: 10.1021/jp062735h.