Excimer Formation in Carboxylic Acid-Functionalized Perylene Diimides Attached to Silicon Dioxide Nanoparticles

Gorman, J.A.; Pandya, Raj; Allardice, Jesse R.; Price, Michael B.; Schmidt, Timothy W.; Friend, Richard H.; Rao, Akshay; Davis, Nathaniel J. L. K.

doi:10.1021/acs.jpcc.8b12061

Cited by 23 publications

(37 citation statements)

References 71 publications

(153 reference statements)

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“…19,20 The same is also true for regular perylenes, 21 which are often used as blue emitters and for triplet−triplet annihilation applications. 22,23 The transitions associated with the lowest energy excitonic states are critical to the performance of organic photonic devices, 19,24,25 with deactivation and quenching by dimer 26,27 or excimer 28,29 states able to outcompete many desired processessuch as charge transfer and transport, 30 exciton diffusion, 31 and intersystem crossing. 26,27,32 PDIs that form such excimer, dimer, or aggregate states also often exhibit significantly different photophysical properties compared to isolated molecules, making understanding and developing device applications complicated at higher concentrations.…”

Section: ■ Introductionmentioning

confidence: 99%

Silylethynyl Substitution for Preventing Aggregate Formation in Perylene Diimides

Aksoy

Danos

et al. 2021

J. Phys. Chem. C

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Ethynylene-bridged perylene diimides (PDIs) with different sized silane groups have been synthesized as a steric blocking group to prevent the formation of non-radiative trap sites, for example, strong H-aggregates and other dimers or excimers. Excited singlet-state exciton dynamics were investigated by time-resolved photoluminescence and ultrafast pump–probe transient absorption spectroscopy. The spectra of the excimer or dimer aggregates formed by the PDIs at high concentrations were also determined. Although the photophysical properties of the bare and shielded PDIs are identical at micromolar concentrations, more shielded PDI2 and PDI3 exhibited resistance to aggregation, retaining higher photoluminescence quantum yield even at 10 mM concentration and in neat films. The PDIs also exhibited high photostability (1 h of continuous excitation), as well as electrochemical stability (multiple cycles with cyclic voltammetry). Prevention of dimer/aggregate formation in this manner will extend the uses of PDIs to a variety of high concentration photonics and optoelectronic applications, such as organic light-emitting diodes, organic photovoltaics, and luminescent solar concentrators.

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Section: ■ Introductionmentioning

confidence: 99%

Silylethynyl Substitution for Preventing Aggregate Formation in Perylene Diimides

Aksoy

Danos

et al. 2021

J. Phys. Chem. C

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“…Excimers can form when chromophores are cofacially stacked, resulting in strong electronic and excitonic coupling, and SB-CS can occur when strong CT interactions are dominant . Perylene − and perylene-based chromophores such as perylenediimides − (PDIs) as well as their longer homologue terrylenediimides , (TDIs) are often used to study photoinduced SB-CS and excimer formation. These and related chromophores ,− are good model compounds to study the balance and interplay between different types of interchromophore coupling that determine the fate of the electronic excited state.…”

Section: Introductionmentioning

confidence: 99%

Excited-State Dynamics of Perylene-Based Chromophore Assemblies on Nanoporous Anodic Aluminum Oxide Membranes

et al. 2021

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Exploring excited-state decay pathways in organic chromophore assemblies often requires significant synthetic effort to systematically change interchromophore distances. Moreover, the solubility of these assemblies is often limited. Herein, we examine how nanoporous anodic aluminum oxide (AAO) membranes can address both of these issues by covalently attaching 3-(phenylethynyl)perylene (PEP) and 1,6,7,12-tetrakis-(4-tert-butylphenoxy)perylene(3,4:9,10)-bis(dicarboximide) (tpPDI) chromophores with different loadings to AAO membranes, where the estimated average distance between chromophores on the AAO membranes for PEP-AAO-1, -2, and -3 is 5, 8, and 16 Å, respectively, while that between tpPDI cores in tpPDI-AAO-1, -2, -3, and -4 is 4, 6, 10, and 17 Å, respectively. When PEP-AAO-1, -2, and -3 are photoexcited, we observe a distribution of excimer-like states with varying degrees of charge-transfer (CT) character depending on the interchromophore spacing and solvent polarity. Increasing solvent polarity or decreasing the interchromophore distance increases the CT character in the excimer state. Notably, a PEP excimer state having significant CT character still forms in air, that is, in the absence of solvent. In contrast, when tpPDI-AAO-1 is photoexcited in solvents of varying polarity, as well as in air, we observe full symmetry-breaking charge separation (SB-CS) between tpPDIs attached to the AAO membrane. The SB-CS and charge recombination rates increase with increasing solvent polarity as the energy of the CT state is lowered. As the average distance between the tpPDIs increases in the series tpPDI-AAO-1, -2, -3, and -4, the SB-CS rate decreases with no SB-CS observed in tpPDI-AAO-4. This demonstrates the utility of AAO membranes to control the fate of electronic excited states by tuning the various contributions from Coulombic and charge transfer coupling.

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“…The high concentration of anthracene functional groups in the solid state, or concentrated around the surface of a nanocrystal, would provide the optimal conditions for excimer formation. 70 A similar display of excimer emission is also observed in many of the PbX2-ACAAX thin-films. After a year of storage in a sealed vial with anhydrous toluene, the sample still fluoresced, indicating a high level of stability.…”

Section: Photoluminescence Of Open-air Synthesised Cspbbr3-ahpacsupporting

confidence: 56%

Functionalisation of Lead Halide Perovskites with Anthracene

Hardy¹

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<b>After only a decade’s worth of research and development, lead halide perovskites are set to become the basis of a new generation of cheap and highly efficient photovoltaic devices. However, traditional lead halide perovskites such as methylammonium lead triiodide or formamidinium lead triiodide suffer from an intolerance to moisture and high temperatures. 2D Ruddlesden-Popper lead halide perovskites and all inorganic caesium lead halide perovskites have gained attention in recent years due to their improved stability with respect to these environmental conditions. </b><p>Like all solar cell technologies, simple lead halide perovskite solar cells have a theoretical maximum efficiency limit of around 30%. Coupling organic fluorophores to semiconducting nanomaterials is a potential route to circumventing and exceeding this efficiency limit. In this work attempts are made to couple anthracene functional groups to 2D Ruddlesden-Popper lead halides and caesium lead trihalide perovskites. The results of this study show that energy transfer does occur between anthracene and caesium lead trihalide nanocrystals, resulting in increased perovskite emission. These results show that organic fluorophores can be utilised in conjunction with perovskite semiconductors, opening up the possibility of circumventing efficiency limits for perovskite photovoltaic technologies. </p>

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Excimer Formation in Carboxylic Acid-Functionalized Perylene Diimides Attached to Silicon Dioxide Nanoparticles

Cited by 23 publications

References 71 publications

Silylethynyl Substitution for Preventing Aggregate Formation in Perylene Diimides

Silylethynyl Substitution for Preventing Aggregate Formation in Perylene Diimides

Excited-State Dynamics of Perylene-Based Chromophore Assemblies on Nanoporous Anodic Aluminum Oxide Membranes

Functionalisation of Lead Halide Perovskites with Anthracene

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