Catharina Hippius

Polymer glass transitions switch electron transfer in individual molecules

Essentially complete photoinduced electron transfer quenching of the fluorescence of a perylene-calixarene compound occurs in poly(methyl acrylate) and poly(vinyl acetate) above their glass transition temperatures (T(g)), but the fluorescence is completely recovered upon cooling the polymer matrix to a few degrees below the T(g). The switching can be observed in an on/off fashion at the level of individual molecules.

Single molecule studies of calix[4]arene-linked perylene bisimide dimers: relationship between blinking, lifetime and/or spectral fluctuations

We recorded fluorescence time traces, and simultaneously either the fluorescence lifetime or the emission spectra from single perylene bisimide (PBI) dimers embedded in a polystyrene matrix. In these traces three distinct intensity levels can be distinguished, which reflect the photo-induced radicalisation of one of the perylene subunits. Differences in the energy transfer rate between the neutral PBI and the reversibly formed radical anion give rise to variations in the chronological order of the appearance of the intensity levels, which allowed us to categorise the time traces into three distinct groups: Type 1 blinking corresponds to a high energy transfer rate, type 2 blinking to fluctuations between large and small transfer rates (dynamic quenching), and type 3 blinking results from small energy transfer rates together with Coulomb blockade. The information that we obtain from the distributions of the fluorescence lifetimes at the various signal levels allows us to relate these differences to properties of the local polymer environment of the dimers.

Stepwise decrease of fluorescence versus sequential photobleaching in a single multichromophoric system.

For individual molecules from the newly synthesized calix[4]arene tethered perylene bisimide (PBI) trimer, we studied the emitted fluorescence intensity as a function of time. Owing to the zigzag arrangement of PBI dyes in these trimers, the polarization state of the emission provides directly information about the emitting subunit within the trimer. Interestingly, we observed emission from all neutral subunits within a trimer rather than exclusively from the subunit with the lowest site energy. This can be understood in terms of thermally activated uphill energy transfer that repopulates the higher energetic chromophores. Together with the simultaneously recorded polarization-resolved emission spectra, this reveals that the emission from a multichromophoric system is governed by a complex interplay between the temporal variations of the photophysical parameters of the subunits, bidirectional hopping processes within the trimer, and unavoidable photobleaching. Moreover, it is demonstrated that the typically observed stepwise decrease of the signal from a multichromophoric system does not necessarily reflect sequential bleaching of the individual chromophores within the macromolecule.

A multi-property fluorescent probe for the investigation of polymer dynamics near the glass transition

In addition to the commonly observed single molecule fluorescence intensity fluctuations due to molecular reorientation dynamics, a perylene bisimide-calixarene compound (1) shows additional on-off fluctuations due to its ability to undergo intramolecular excited state electron transfer (PET). This quenching process is turned on rather sharply when a film of poly(vinylacetate) containing 1 is heated above its glass transition temperature (Tg), which indicates that the electron transfer process depends on the availability of sufficient free volume. Spatial heterogeneities cause different individual molecules to reach the electron transfer regime at different temperatures, but these heterogeneities also fluctuate in time: in the matrix above Tg molecules that are mostly nonfluorescent due to PET can become fluorescent again on timescales of seconds to minutes.The two different mechanisms for intensity fluctuation, rotation and PET, thus far only observed in compound 1, make it a unique probe for the dynamics of supercooled liquids.

5-Bromo-17-nitro-26,28-prop-2-en-oxy-25,27-dipropoxycalix[4]arene.

Molecules of the title compound, C40H42BrNO6, are located on a crystallographic twofold rotation axis. As a result, the nitro group and bromine residue are mutually disordered with equal occupancies. The propoxy-substituted aromatic rings are close to parallel to each other [dihedral angle = 21.24 (1)°], whereas the propenoxy-substituted rings enclose a dihedral angle of 70.44 (1)°. The dihedral angles between the methylene C atoms and the aromatic rings shows that the propenoxy substituted rings are bent away from the calixarene cavity [dihedral angle between the planes = 35.22 (8)°], whereas the propoxy-substituted rings are almost perpendicular [79.38 (10)°] to the plane of the methylene C atoms.