Diketopyrrolopyrrole based molecular materials : synthesis, optical characterization, and application in photovoltaics

Organic p-conjugated oligomers and polymers are versatile materials for application in optoelectronics, e.g. photovoltaic cells. The electronic structure of the lower excited states in these materials, which determine the optoelectronic properties, can be controlled by distinct synthetic design. The strategy used throughout the thesis, consists of design, modification, synthesis and optical characterization of well known diketopyrrolopyrrole (DPP) and isodiketopyrrolopyrrole (iDPP) low molecular weight materials and p-conjugated polymers

Sodium and Potassium Ion Selective Conjugated Polymers for Optical Ion Detection in Solution and Solid State

EPSRC. Grant Number: EP/G037515/1; EC FP7 Project SC2. Grant Number: 610115; EC FP7 Project ArtESun. Grant Number: 604397; EC FP7 POLYMED. Grant Number: 61253

Intramolecular excimer formation between 3,6-Di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione chromophoric groups linked by a flexible alkyl spacer

Bichromophoric molecules containing two 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) moieties linked via aliphatic spacers of different length are synthesized. Optical absorption spectroscopy indicates that the molecules adopt an extended conformation in solution. Fluorescence spectroscopy shows that photons are emitted from the locally excited singlet state in an extended conformation. In sufficiently polar solvents, quenching of fluorescence occurs and fluorescence quantum yield (FF) and fluorescence lifetime (tF) measurements indicate formation of an intramolecular excimer as the quenching mechanism. The redox potentials of the molecules and the solvent polarity dependence of the quenching are consistent with significant charge-transfer character of the excimer state. Photoinduced absorption measurements show enhanced intersystem crossing to the triplet state in polar solvents. Results indicate that in donor–acceptor p-conjugated materials involving the DPP moiety, excimer-like interchain polaron pair excited states could play an important role in the photophysics because of their close proximity in energy to the lowest singlet excited

Optical properties of oligothiophene substituted diketopyrrolopyrrole derivatives in solid phase : joint J and H-type aggregation

Photophysical properties of diketopyrrolopyrrole derivatives substituted with oligothiophenes are investigated. All compounds are found to be fluorescent both in solution and in the solid phase. At low temperature in the solid, fluorescence originates from excimer-like excited states. Comparison of absorption and fluorescence excitation spectra taken under matrix isolated conditions and on solid films show the presence of both J- and H-type absorption bands in the solid phase. Quantum-chemical calculations, including exciton-phonon coupling to account for deviations from the Born-Oppenheimer approximation, are performed to simulate the band shape of the lowest absorption band in the molecular solid. The joint presence of J- and H-bands is explained by the presence of two molecules in the unit cell. The Davydov splitting is substantial for molecules with linear alkyl substituents on the nitrogen atom (on the order of 0.2 eV) but can be reduced to almost zero by introducing branching at the ß-carbon of the alkyl side chain

Optical properties of oligothiophene substituted diketopyrrolopyrrole derivatives in solid phase : joint J and H-type aggregation

Photophysical properties of diketopyrrolopyrrole derivatives substituted with oligothiophenes are investigated. All compounds are found to be fluorescent both in solution and in the solid phase. At low temperature in the solid, fluorescence originates from excimer-like excited states. Comparison of absorption and fluorescence excitation spectra taken under matrix isolated conditions and on solid films show the presence of both J- and H-type absorption bands in the solid phase. Quantum-chemical calculations, including exciton-phonon coupling to account for deviations from the Born-Oppenheimer approximation, are performed to simulate the band shape of the lowest absorption band in the molecular solid. The joint presence of J- and H-bands is explained by the presence of two molecules in the unit cell. The Davydov splitting is substantial for molecules with linear alkyl substituents on the nitrogen atom (on the order of 0.2 eV) but can be reduced to almost zero by introducing branching at the ß-carbon of the alkyl side chain

Photophysics of Self-Assembled Monolayers of a π-Conjugated Quinquethiophene Derivative

The photophysics of fully and partially covered self-assembled monolayers (SAMs) of a quinquethiophene (5T) derivative have been investigated. The monolayers behave as H-aggregates. The fluorescence of fully covered SAMs is weak and red-shifted, and the extinction is blue-shifted as compared to that of single molecules. The fluorescence of partially covered SAMs is dominated by that of single molecules on the surface. The extinction spectra are similar for fully and partially covered monolayers, which show that even the smallest islands are H-aggregates. The extinction spectra furthermore closely resemble those for 5T single crystals, which demonstrates that in oligothiophene crystals the intermolecular interactions within one layer molecules are stronger than the interlayer electronic coupling.

Synthesis and optical properties of Pyrrolo[3,2-b]pyrrole-2,5(1H,4H)-dione (iDPP)-based molecules

We describe the synthesis and photophysical properties of a series of derivatives of pyrrolo[3,2-b]pyrrole-2,5(1H,4H)-dione-3,6-diyl (iDPP) linked to two oligothiophenes of variable length (nT). The iso-DPP-oligothiophenes (iDPPnTs) differ from the common pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-3,6-diyl-oligothiophene analogues (DPPnTs) by a different orientation of the two lactam rings in the bicyclic iDPP unit compared to DPP. In contrast to the highly fluorescent DPPnTs, the new isomeric iDPPnTs exhibit only very weak fluorescence. We demonstrate with the help of quantum-chemical calculations that this can be attributed to a different symmetry of the lowest excited state in iDPPnT (A in C2 symmetry) compared to DPPnTs (B) and the corresponding loss in oscillator strength of the lowest energy transition. Upon extending the oligothiophene moiety in the iDPPnTs molecules, the charge transfer character of the lowest A excited state becomes more pronounced. This tends to preclude high fluorescence quantum yields even in extended iDPPnTs systems