Probing electronic communication for efficient light-harvesting functionality: dyads containing a common perylene and a porphyrin, chlorin, or bacteriochlorin.
J Phys Chem B
; 118(6): 1630-47, 2014 Feb 13.
Article
in En
| MEDLINE
| ID: mdl-24484243
ABSTRACT
The synthesis, photophysical, redox, and molecular-orbital characteristics of three perylene-tetrapyrrole dyads were investigated to probe the efficacy of the arrays for use as light-harvesting constituents. Each dyad contains a common perylene-monoimide that is linked at the N-imide position via an arylethynyl group to the meso-position of the tetrapyrrole. The tetrapyrroles include a porphyrin, chlorin, and bacteriochlorin, which have zero, one, and two reduced pyrrole rings, respectively. The increased pyrrole-ring reduction results in a progressive red shift and intensification of the lowest-energy absorption band, as exemplified by benchmark monomers. The arylethyne linkage affords moderate perylene-tetrapyrrole electronic coupling in the dyads as evidenced by the optical, molecular-orbital, and redox properties of the components of the dyads versus the constituent parts. All three dyads in nonpolar solvents exhibit relatively fast (subpicosecond) energy transfer from the perylene to the tetrapyrrole. Competing charge-transfer processes are also absent in nonpolar solvents, but become active for both the chlorin and bacteriochlorin-containing dyads in polar solvents. Calculations of energy-transfer rates via the Förster, through-space mechanism reveal that these rates are, on average, 3-fold slower than the observed rates. Thus, the Dexter through-bond mechanism contributes more substantially than the through-space mechanism to energy transfer in the dyads. The electronic communication between the perylene and tetrapyrrole falls in a regime intermediate between those operative in other classes of perylene-tetrapyrrole dyads that have previously been studied.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Perylene
/
Porphyrins
/
Electrons
/
Energy Transfer
/
Light
Type of study:
Prognostic_studies
Language:
En
Journal:
J Phys Chem B
Journal subject:
QUIMICA
Year:
2014
Document type:
Article
Affiliation country:
United States