Energy Migration in Dendritic Oligothiophene-Perylene Bisimides
ABSTRACT A series of novel oligothiophene-perylene bisimide hybrid (DOTPBI) dendrimers up to the second generation (G0, G1, and G2) were investigated. Optical measurements such as nonlinear optical and time-resolved spectroscopy, including two-photon absorption, fluorescence upconversion, and excited state transient absorption were carried out. Results of these measurements revealed the ability of these molecules to undergo intramolecular fluorescence resonance energy transfer (FRET) from the dendritic oligothiophenes (DOT) to the perylene bismide (PBI) moiety. The delocalization length and the photoinduced electron transfer (PET) rate were investigated as a function of dendrimer generation. A fast energy transfer process from the DOT dendron to the PBI core was observed. For the case of the G2 dendrimer, with relatively large thiophene dendrons attached to the bay area of the perylene bisimide, the PBI core is highly twisted and its ability to self-assemble into π-π stacked aggregates is destroyed. As a result, among the three generations studied, G1, which has the best two-photon cross section and the most efficient energy transfer, is the best light harvesting material.
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ABSTRACT: Two new soluble tri-tert-butyl zinc(II) phthalocyanines, 1 and 2, bearing dendritic oligothienylene-ethynylene (DOT) groups as one of the peripheral substituents, have been prepared. The conjugated DOT moieties were introduced to cover the spectral window between 380 and 550 nm, where the ZnPc does not exhibit a strong absorption, in order to improve light harvesting. For their preparation, a convergent approach has been used starting from the corresponding iodoPc as precursor. Further transformation of the iodo groups by a Pd-catalyzed Sonogashira reaction with the appropriate DOT-functionalized terminal alkyne allowed the easy preparation of extended π-conjugated compounds 1 and 2. The compounds have been characterized by standard spectroscopic methods, and their photophysical behaviors have been established by using ultrafast time-resolved techniques. Femtosecond upconversion measurements showed an ultrafast energy transfer from the DOT to zinc phthalocyanine in a time scale of 300 fs. As the number of thiophene groups increases in the dyads, the extent of ultrafast energy transfer was found to increase. Compounds 1 and 2 have been tested as donor components in bulk heterojunction (BHJ) solar cells. Their efficiencies are compared with RuPc analogues previously reported by us.The Journal of Physical Chemistry C 09/2013; 117(40). DOI:10.1021/jp404406b · 4.84 Impact Factor
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ABSTRACT: The fundamental theory of processes and properties associated with nanoscale photonics should properly account for the quantum nature of both the matter and the radiation field. A familiar example is the Casimir force, whose significant role in nanoelectromechanical systems is widely recognised; the correct representation invokes the creation of short-lived virtual photons from the vacuum. In fact, there is an extensive range of nanophotonic interactions in which virtual photon exchange plays a vital role, mediating the coupling between particles. This review surveys recent theory and applications, also exhibiting novel insights into key electrodynamic mechanisms. Examples are numerous and include: laser-induced inter-particle forces known as optical binding; non-parametric frequency-conversion processes especially in rare-earth doped materials; light-harvesting polymer materials that involve electronic energy transfer between their constituent chromophores. An assessment of these and the latest prospective applications concludes with a view on future directions of research.Annalen der Physik 04/2014; 526(3-4). DOI:10.1002/andp.201300219 · 1.48 Impact Factor
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ABSTRACT: Two generations of highly emissive conjugated anthracene dendrimers containing up to 9 anthracene units are presented. In these dendrimers, anthracene-like absorption and emission properties are preserved due to the relatively weak electronic coupling between the anthracene units, while evidence of a fast crosstalk within the molecular framework is still observed.RSC Advances 04/2014; 4(38). DOI:10.1039/C4RA02341B · 3.71 Impact Factor