Matrix-induced linear Stark effect of single dibenzoterrylene molecules in 2,3-dibromonaphthalene crystal

Absorption and fluorescence from single molecules can be tuned by applying an external electric field – a phenomenon known as the Stark effect. A linear Stark effect is associated to a lack of centrosymmetry of the guest in the host matrix. Centrosymmetric guests can display a linear Stark effect in disordered matrices, but the response of individual guest molecules is often relatively weak and non‐uniform, with a broad distribution of the Stark coefficients. Here we introduce a novel single‐molecule host‐guest system, dibenzoterrylene (DBT) in 2,3‐dibromonaphthalene (DBN) crystal. Fluorescent DBT molecules show excellent spectral stability with a large linear Stark effect, of the order of 1.5 GHz/kVcm−1, corresponding to an electric dipole moment change of around 2 D. Remarkably, when the electric field is aligned with the a crystal axis, nearly all DBT molecules show either positive or negative Stark shifts with similar absolute values. These results are consistent with quantum chemistry calculations. Those indicate that DBT substitutes three DBN molecules along the a‐axis, giving rise to eight equivalent embedding sites, related by the three glide planes of the orthorhombic crystal. The static dipole moment of DBT molecules is created by host‐induced breaking of the inversion symmetry. This new host–guest system is promising for applications that require a high sensitivity of fluorescent emitters to electric fields, for example to probe weak electric fields

Reverse intersystem crossing of single deuterated perylene molecules in a dibenzothiophene matrix

Biological and Soft Matter Physic

Solvatofluorochromic, non-centrosymmetric π-expanded diketopyrrolopyrrole

A novel non-centrosymmetric π-expanded diketopyrrolopyrrole was designed and synthesized. Strategic placement of tert-butyl groups at the periphery of a diketopyrrolopyrrole allowed us to selectively fuse one moiety via tandem Friedel–Crafts-dehydration reactions, resulting in a non-centrosymmetric dye. The structure of the dye was confirmed by X-ray crystallography, revealing that it contains a nearly flat arrangement of four fused rings. Extensive photophysical studies of this new functional dye revealed that the intensity of its emission strongly depends on solvent polarity, which is typical for dipolar chromophores. In non-polar solvents, the fluorescence quantum yield is high whereas in polar solvents such as MeOH, it is 12%. However, upon two-photon excitation the compound behaves like a centrosymmetric dye, showing a two-photon absorption maximum at significantly shorter wavelengths than twice the wavelength of the one-photon absorption maximum

Symmetry Breaking in Pyrrolo[3,2-b]pyrroles: Synthesis, Solvatofluorochromism and Two-photon Absorption

Five centrosymmetric and one dipolar pyrrolo[3,2-b]pyrroles, possessing either two or one strongly electron-withdrawing nitro group have been synthesized in a straightforward manner from simple building blocks. For the symmetric compounds, the nitroaryl groups induced spontaneous breaking of inversion symmetry in the excited state, thereby leading to large solvatofluorochromism. To study the origin of this effect, the series employed peripheral structural motifs that control the degree of conjugation via altering of dihedral angle between the 4-nitrophenyl moiety and the electron-rich core. We observed that for compounds with a larger dihedral angle, the fluorescence quantum yield decreased quickly when exposed to even moderately polar solvents. Reducing the dihedral angle (i.e., placing the nitrobenzene moiety in the same plane as the rest of the molecule) moderated the dependence on solvent polarity so that the dye exhibited significant emission, even in THF. To investigate at what stage the symmetry breaking occurs, we measured two-photon absorption (2PA) spectra and 2PA cross-sections (sigma(2PA)) for all six compounds. The 2PA transition profile of the dipolar pyrrolo[3,2-b]pyrrole, followed the corresponding one-photon absorption (1PA) spectrum, which provided an estimate of the change of the permanent electric dipole upon transition, approximate to 18D. The nominally symmetric compounds displayed an allowed 2PA transition in the wavelength range of 700-900nm. The expansion via a triple bond resulted in the largest peak value, sigma(2PA)=770GM, whereas altering the dihedral angle had no effect other than reducing the peak value two- or even three-fold. In the S0S1 transition region, the symmetric structures also showed a partial overlap between 2PA and 1PA transitions in the long-wavelength wing of the band, from which a tentative, relatively small dipole moment change, 2-7D, was deduced, thus suggesting that some small symmetry breaking may be possible in the ground state, even before major symmetry breaking occurs in the excited state.1111Ysciescopu

L\'evy Distribution of Single Molecule Line Shape Cumulants in Low Temperature Glass

We investigate the distribution of single molecule line shape cumulants, $\kappa_1,\kappa_2,...$, in low temperature glasses based on the sudden jump, standard tunneling model. We find that the cumulants are described by L\'evy stable laws, thus generalized central limit theorem is applicable for this problem.Comment: 5 pages, 3 figure

Single molecules detect ultra-slow oscillators in a molecular crystal excited by ac-voltages

Biological and Soft Matter Physic

Fluctuations in the emission polarization and spectrum in single chains of a common conjugated polymer for organic photovoltaics

Measuring the nanoscale organization of conjugated polymer chains used in organic photovoltaic (OPV) blends is vital if one wants to understand the materials. This is made very difficult with high efficiency OPV polymers such as PTB7 that form aggregates, as a lack of periodicity and a high degree of disorder make understanding of the nanoscale organization challenging. Here, single molecule spectroscopy is used to observe single chains and aggregates of PTB7. Using four detectors the photoluminescence intensity, wavelength, polarization, and lifetime are simultaneously monitored. Fast (milliseconds) and slow (seconds) fluctuations are observed over a time window of 30 s in all of these observables from single aggregates and chains as individual chromophores activate and deactivate, leading to dynamical changes in the emission spectrum and dipole orientation. This information can be used to help reconstruct the spatial and spectral organization of disordered aggregates of PTB7, thereby adding valuable new information on how the chains are arranged in space

Visualisation system based on image warping and delaunay triangulation of the space

In this article we present a visualisation algorithm based on image warping. A source data for the algorithm is a set of images with colour and depth information rendered for the observer located in a number of reference positions. For each position there are 6 images rendered for the directions of axes forming the "image cube". The algorithm computes a 3D Delaunay triangulation on these positions and divides the space inside the convex hull into tetrahedra. During the visualisation process the observer situated in one tetrahedron sees warped images from the vertices of this tetrahedron. We also describe the automatic algorithm for selection of new reference positions to improve the quality and remove "holes". For both algorithms we utilize 3D hardware acceleration