Structure and photophysics of indigoids for singlet fission: Cibalackrot

We report an investigation of structure and photophysics of thin layers of cibalackrot, a sturdy dye derived from indigo by double annulation at the central double bond. Evaporated layers contain up to three phases, two crystalline and one amorphous. Relative amounts of all three have been determined by a combination of X-ray diffraction and FT-IR reflectance spectroscopy. Initially, excited singlet state rapidly produces a high yield of a transient intermediate whose spectral properties are compatible with charge-transfer nature. This intermediate more slowly converts to a significant yield of triplet, which, however, does not exceed 100% and may well be produced by intersystem crossing rather than singlet fission. The yields were determined by transient absorption spectroscopy and corrected for effects of partial sample alignment by a simple generally applicable procedure. Formation of excimers was also observed. In order to obtain guidance for improving molecular packing by a minor structural modification, calculations by a simplified frontier orbital method were used to find all local maxima of singlet fission rate as a function of geometry of a molecular pair. The method was tested at 48 maxima by comparison with the ab initio Frenkel-Davydov exciton model. Published under license by AIP Publishing

Singlet fission rate : optimized packing of a molecular pair : ethylene as a model

A procedure is described for unbiased identification of all pi-electron chromophore pair geometry choices that locally maximize the rate of conversion of a singlet exciton into a singlet biexciton (triplet pair), using a simplified version of the diabatic frontier orbital model of singlet fission (SF). The resulting approximate optimal geometries provide insight and are expected to represent useful starting points for searches by more advanced methods. The general procedure is illustrated on a pair of ethylenes as the simplest model of a pi-electron system, but it is applicable to pairs of much larger molecules, with dozens of non-hydrogen atoms, and not necessarily planar. We first examine the value of vertical bar T-A vertical bar(2), the square of the electronic matrix element for SF with initial excitation fully localized on partner A, on a grid of several billion geometries within the six-dimensional space of physically realizable possibilities. Several of the optimized pair geometries are somewhat unexpected, but all are found to follow the qualitative guidance proposed earlier. In the neighborhood of each local maximum of vertical bar T-A vertical bar(2), consideration of mixing with charge-transfer configurations and of excitonic interaction between partners A and B determines the SF energy balance and yields squared matrix elements vertical bar T*vertical bar(2) and vertical bar T**vertical bar(2) for the lower and upper excitonic states S* and S**, respectively. Assuming Boltzmann populations of these states, the geometry is further optimized to maximize k, the sum of the SF rates obtained from Marcus theory, and this reorders the suitable geometries substantially. At 87 pair geometries, the vertical bar T*vertical bar(2) and vertical bar T**vertical bar(2) values are compared with those obtained from high-level ab initio nonorthogonal configuration interaction calculations and found to follow the same trend. Finally, the biexciton binding energy at the optimized geometries is calculated. Altogether, 13 significant local maxima of SF rate for a pair of ethylenes are identified in the physically relevant part of space that avoids molecular interpenetration in the hard-sphere approximation. The three best geometries are twist-stacked, slip-stacked, and L-shaped. The maxima occur at the (five dimensional) surfaces of seven six-dimensional "parent" regions of space centered at physically inaccessible geometries at which the calculated SF rate is very large but the two ethylenes interpenetrate. The results are displayed in interactive graphics. The computer code ("Simple") written for these calculations is flexible in that it permits a choice of performing the search for local maxima in six dimensions on vertical bar T-A vertical bar(2), vertical bar T*vertical bar(2), or k

Phenyl-Substituted Cibalackrot Derivatives: Synthesis, Structure, and Solution Photophysics

Three symmetrically and three unsymmetrically substituted cibalackrot (7,14-diphenyldiindolo[3,2,1-de:3\u27,2\u27,1\u27-ij][1,5]naphthyridine-6,13-dione, 1) dyes carrying two derivatized phenyl rings have been synthesized as candidates for molecular electronics and especially for singlet fission, a process of interest for solar energy conversion. Solution measurements provided singlet and triplet excitation energies and fluorescence yields and lifetimes; conformational properties were analyzed computationally. The molecular properties are close to ideal for singlet fission. However, crystal structures, obtained by single-crystal X-ray diffraction, are rather similar to those of the polymorphs of solid 1, in which formation of a charge-separated state followed by intersystem crossing, complemented with excimer formation, outcompetes singlet fission. Results of calculations by the approximate SIMPLE method suggest which ones among the solid derivatives are the best candidates for singlet fission, but it appears difficult to change the crystal packing in a desirable direction. We also describe the preparation of three specifically deuteriated versions of 1, expected to help sort out the mechanism of fast intersystem crossing in its charge-separated state

Phenyl-Substituted Cibalackrot Derivatives: Synthesis, Structure, and Solution Photophysics

Three symmetrically and three unsymmetrically substituted cibalackrot (7,14-diphenyldiindolo[3,2,1-de:3',2',1'-ij][1,5]naphthyridine-6,13-dione, 1) dyes carrying two derivatized phenyl rings have been synthesized as candidates for molecular electronics and especially for singlet fission, a process of interest for solar energy conversion. Solution measurements provided singlet and triplet excitation energies and fluorescence yields and lifetimes; conformational properties were analyzed computationally. The molecular properties are close to ideal for singlet fission. However, crystal structures, obtained by single-crystal X-ray diffraction (XRD), are rather similar to those of the polymorphs of solid 1, in which the formation of a charge-separated state followed by intersystem crossing, complemented with excimer formation, outcompetes singlet fission. Results of calculations by the approximate SIMPLE method suggest which ones among the solid derivatives are the best candidates for singlet fission, but it appears difficult to change the crystal packing in a desirable direction. We also describe the preparation of three specifically deuteriated versions of 1, expected to help sort out the mechanism of fast intersystem crossing in its charge-separated state

Štěpení singletu v tenkých vrstvách bis(thienyl)diketopyrrolopyrrolů

The singlet fission (SF) process discovered in bis(thienyl)diketopyrrolopyrroles (TDPPs) can boost their potential for photovoltaics (PV). The crystal structures of TDPP analogs carrying n-hexyl, n-butyl, or 2-(adamant-1-yl)ethyl substituents are similar, but contain increasingly slipped stacked neighbor molecules. The observed SF rate constants, k(SF), (7 +/- 4), (9 +/- 3) and (5.6 +/- 1.9) ns(-1) for thin films of the three compounds, respectively, are roughly equal, but the triplet quantum yields vary strongly: (120 +/- 40), (160 +/- 40) and (70 +/- 16), respectively. The recent molecular pair model reproduces the near equality of all three k(SF) at the crystal geometries and identifies all possible pair arrangements in which SF is predicted to be faster, by up to two orders of magnitude. However, it is also clear that the presently non-existent ability to predict the rates of processes competing with SF is pivotal for providing a guide for efforts to optimize the materials for PV.Proces singletového štěpení (SF), objevený u bis(thienyl)diketopyrrolopyrrolů (TDPPs) může posílit jejich potenciál pro fotovoltaiku. Krystalové struktury analog TDPP nesoucí n-hexyl, n-butyl nebo 2-(adamant-1-yl)ethyl skupiny jsou podobné. Pozorovaná rychlostní konstanta singletového štěpení, k(SF), (7+/-4), (9+/-3) a (5,6 +/-1,9) ns-1 pro tenké filmy těchto tří derivátů jsou přibližně rovné, ale tripletové kvantové výtěžky se silně liší: (120+/-40), (160+/- 40), (70+/-16). Nedávný model molekulových párů reprodukuje blízkou rovnost všech tří k(SF) v geometrii krystalu a identifikuje všechna možná uspořádání párů, u nichž se předpokládá, že SF bude asi o 2 řády rychlejší