Dye–dye interactions affect the optical and electronic properties in organic semiconductor films of light harvesting and detecting optoelectronic applications. This review elaborates how to tailor these properties of organic semiconductors for organic solar cells (OSCs) and organic photodiodes (OPDs). While these devices rely on similar materials, the demands for their optical properties are rather different, the former requiring a broad absorption spectrum spanning from the UV over visible up to the near‐infrared region and the latter an ultra‐narrow absorption spectrum at a specific, targeted wavelength. In order to design organic semiconductors satisfying these demands, fundamental insights on the relationship of optical properties are provided depending on molecular packing arrangement and the resultant electronic coupling thereof. Based on recent advancements in the theoretical understanding of intermolecular interactions between slip‐stacked dyes, distinguishing classical J‐aggregates with predominant long‐range Coulomb coupling from charge transfer (CT)‐mediated or ‐coupled J‐aggregates, whose red‐shifts are primarily governed by short‐range orbital interactions, is suggested. Within this framework, the relationship between aggregate structure and functional properties of representative classes of dye aggregates is analyzed for the most advanced OSCs and wavelength‐selective OPDs, providing important insights into the rational design of thin‐film optoelectronic materials.
A series of 1-mono-and 1,7-disubstituted perylene bisimides (PBIs) with voluminous phenoxy groups at bay positions has been synthesized. These dyes show absorption and emission properties typical for PBIs in solution with high fluorescence quantum yields close to unity. In the solid state, the voluminous substituents at bay positions effectively wrap the dye core and prevent π−π interactions between twofold substituted chromophores. The comparison of UV−vis absorption and fluorescence properties for solutions as well as solid-state thin films, powders, and microcrystals in combination with the respective singlecrystal structures allows for establishing the packing structure−optical property relationships. According to this analysis, only with two bulky 2,4,6-tris(4-tertbutylphenyl)-phenoxy or 2,4,6-tris(3,5-di-tert-butylphenyl)-phenoxy substituents functionalized PBI chromophores are completely jacketed to afford efficient solid-state emitter materials with fluorescence quantum yields of over 60%. A comparative evaluation of PBIs bearing bulky substituents at imide positions reveals significantly higher solidstate fluorescence quantum yields of the 1,7-substituted PBIs.
Magnetic
particle spectroscopy (MPS) is used in this work to obtain
a magnetic fingerprint signal from anisotropic supraparticles, i.e.,
microrods assembled from superparamagnetic iron oxide nanoparticles.
Exceeding its intended purpose of nanoparticle characterization for
biomedical magnetic particle imaging, it is shown that MPS is capable
of resolving structural differences between the anisotropic alignment
of individual nanoparticles and its isotropic counterpart. Additionally,
orientation-dependent MPS signal variations of anisotropic supraparticles
are identifiable. This finding enables the detection of cold-chain
breaches (for instance, during delivery of a product that needs to
be cooled all of the time) by recording the initial and final MPS
signals of microrod samples integrated into the container of a frozen
product.
Dye arrays from dimers up to larger oligomers constitute the functional units of natural light harvesting systems as well as organic photonic and photovoltaic materials. Whilst in the past decades many photophysical studies were devoted to molecular dimers for deriving structure-property relationship to unravel the design principles for ideal optoelectronic materials, they fail to accomplish the subsequent processes of charge carrier generation or the detachment of two triplet species in singlet fission (SF). Here, we present a slip-stacked perylene bisimide trimer, which constitutes a bridge between hitherto studied dimer and solid-state materials, to investigate SF mechanisms. This work showcases multiple pathways towards the multiexciton state through direct or excimer-mediated mechanisms by depending upon interchromophoric interaction. These results suggest the comprehensive role of the exciton coupling, exciton delocalization, and excimer state to facilitate the SF process. In this regard, our observations expand the fundamental understanding the structure-property relationship in dye arrays.
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