Salt-induced thermochromism of a conjugated polyelectrolyte

We report here the photophysical properties of a water-soluble conjugated polythiophene with cationic side-chains. When dissolved in aqueous buffer solution (PBS, phosphate buffered saline), there is ordering of the polymer chains due to the presence of the salts, in contrast to pure water, where a random-coil conformation is adopted at room temperature. The ordering leads to a pronounced colour change of the solution (the absorption maximum shifts from 400 nm to 525 nm). Combining resonance Raman spectroscopy with density functional theory computations, we show a significant backbone planarization in the ordered phase. Moreover, the ratio of ordered phase to random-coil phase in PBS solution, as well as the extent of intermolecular interactions in the ordered phase, can be tuned by varying the temperature. Femtosecond transient absorption spectroscopy reveals that the excited- state behaviour of the polyelectrolyte is strongly affected by the degree of ordering. While triplet state formation is favoured in the random-coil chains, the ordered chains show a weak yield of polarons, related to interchain interactions. The investigated polyelectrolyte has been previously used as a biological DNA sensor, based on optical transduction when the conformation of the polyelectrolyte changes during assembly with the biomolecule. Therefore, our results, by correlating the photophysical properties of the polyelectrolyte to backbone and intermolecular conformation in a biologically relevant buffer, provide a significant step forward in understanding the mechanism of the biological sensing

Structural and photophysical templating of conjugated polyelectrolytes with single-stranded DNA

A promising approach to influence and control the photophysical properties of conjugated polymers is directing their molecular conformation by templating. We explore here the templating effect of single-stranded DNA oligomers (ssDNAs) on cationic polythiophenes with the goal to uncover the intermolecular interactions that direct the polymer backbone conformation. We have comprehensively characterized the optical behavior and structure of the polythiophenes in conformationally distinct complexes depending on the sequence of nucleic bases and addressed the effect on the ultrafast excited-state relaxation. This, in combination with molecular dynamics simulations, allowed us a detailed atomistic-level understanding of the structure−property correlations. We find that electrostatic and other noncovalent interactions direct the assembly with the polymer, and we identify that optimal templating is achieved with (ideally 10−20) consecutive cytosine bases through numerous π-stacking interactions with the thiophene rings and side groups of the polymer, leading to a rigid assembly with ssDNA, with highly ordered chains and unique optical signatures. Our insights are an important step forward in an effective approach to structural templating and optoelectronic control of conjugated polymers and organic materials in general

Excited State Dynamics of a Self‐Doped Conjugated Polyelectrolyte

The growing number of applications of doped organic semiconductors drives the development of highly conductive and stable materials. Lack of under- standing about the formation and properties of mobile charges limits the ability to improve material design. Thus the largely unexplored photophysics of doped systems are addressed here to gain insights about the characteris- tics of doping-induced polarons and their interactions with their surround- ings. The study of the ultrafast optical processes in a self-doped conjugated polyelectrolyte reveals that polarons not only affect their environment via Coulomb effects but also strongly couple electronically to nearby neutral sites. This is unambiguously demonstrated by the simultaneous depletion of both the neutral and polaronic transitions, as well as by correlated excited state dynamics, when either transition is targeted during ultrafast experiments. The results contrast with the conventional picture of localized intragap polaron states but agree with revised models for the optical transitions in doped organic materials, which predict a common ground level for polarons and neighboring neutral sites. Such delocalization of polarons into the frontier transport levels of their surroundings could enhance the electronic connectivity between doped and undoped sites, contributing to the formation of conductive charges

Determination of the molecular structure of the short-lived light-induced high-spin state in the spin-crossover compound [Fe(6-mepy)(3)tren](PF6)(2)

In the spin-crossover compound [Fe(6-mepy)(3)tren](PF6)(2), (6-mepy)(3)tren=tris{4-[(6-methyl)-2-pyridyl]-3-aza-butenyl}amine, the high-spin state can be populated as a metastable state below the thermal transition temperature via irradiation into the metal to the ligand charge-transfer absorption band of the low-spin species. At 10 K, the lifetime of thismetastable state is only 1 s. Despite this, it is possible to determine an accurate excited state structure by following the evolution of relevant structural parameters by synchrotron x-ray diffraction under continuous irradiation with increasing intensity. The difference in metal-ligand bond length between the high-spin and the low-spin states is found to be 0.192 angstrom, obtained from an analysis of the experimental data using the mean-field approximation to model cooperative effects

Ln( iii ) complexes with triptycene based tripodal ligands: speciation and equilibria.

International audienceTriaminotriptycene was used as a rigid anchoring platform for preparing several organic ligands for Ln(III) complexation. In this work we present detailed speciation studies with a tripodal ligand L6 possessing terminal carboxamide coordinating moieties. The solution speciation for different [Ln]/[L] ratios is investigated using NMR and mass spectrometry and compared with those of closely related ligands L7 and L8. A special interest is devoted to chemical equilibria in metal excess, whereby different complex species are generated through slow transformations. The effect of the ionic radius along the lanthanide series is discussed for tetranuclear and trinuclear complexes