Diketopyrrolopyrroles Research Articles

Diketopyrrolopyrroles As Performance Enhancing Additives for Lithium-Sulfur Batteries

Although the lithium-ion battery (LIB) has been instrumental in global electrification, more premium applications (such as electrification of aircraft) require capacities and performance beyond the capabilities of traditional LIB chemistries[1]. Lithium-sulfur (Li-S) batteries are a front runner among next generation battery technologies thanks to their very high theoretical capacities (1675 mAh g-1) and impressive gravimetric energy densities (2,700 Wh kg-1) [2,3]. Despite their potential, there are numerous chemical challenges (polysulfide shuttle, dendrite formation etc.) that must be overcome before widespread adoption of the technology [4]. Electrolyte additives have been explored as a means to facilitate the electron transfer reactions that occur within the cell and improve cell capacity and cyclability [5].Diketopyrrolopyrroles (DPPs) are a class of organic π-conjugated compounds that have garnered significant interest in a variety of electrical applications, including solar cells and sensors [6]. The high electrochemical tunability, made possible through the editable organic structure, makes them suitable candidates for redox active electrolyte additives. Here, we explore DPP derivatives as a novel class of electrolyte additive for improving the cell cycling performance of Li-S batteries. A variety of electrochemical and analytical techniques have been utilised to assess the suitability of DPPs as redox active additives, building an understanding of their interactions with active materials in a Li-S cell. Galvanostatic cycling allows us to connect these electrochemical findings to cell cycling performance, where we observe a large enhancement in capacity. We also present an alternative statistical approach to cell data analysis, providing a more concrete method to assessing cycling enhancement than that shown throughout literature. Figure 1. A box plot displaying the discharge capacities at specific cycle numbers for standard (light grey) and DPP (dark grey) cells to provide a statistical comparison.

The Diverse Electrochemistry and Photophysics of Pyrrolopyrroles

Pyrrole is among the most popular molecular scaffolds for biology. Tetrapyrroles, such as porphyrins, corrins and their derivatives, are the quintessential redox centers and chromophores exhibiting a wide range of electrochemical and optical characteristics. Similarly, pyrrolopyrroles, built on condensed five-member rings with nitrogens as heteroatoms, offer scaffolds for organic chromophores with diversity of redox and photophysical properties. For example, pyrrolo[3,2-b]pyrroles are stable electron-rich UV absorbers with quadrupole symmetry (Acc. Chem. Res. 2017, 50, 2334-2345). They can act as immensely potent electron donors and attaching electron-accepting moieties to them leads to the emergence of a myriad of optical phenomena, such as excited-state symmetry breaking (Commun. Chem. 2020, 3, 190) and generating white fluorescence by tuning donor-acceptor electronic coupling (Chem. Sci. 2023). Attaching carbonyls to the pyrrolopyrrole rings drastically changes their electronic properties, making them pronouncedly electron deficient and shifting their absorption to the visible spectral region. For example, 2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-diones, or diketopyrrolopyrroles (DPPs) for short, are excellent electron acceptors and photooxidants (Adv. Opt. Matter. 2015, 3, 2018-320). Their reduction potentials are susceptible to localized electric fields, which has allowed demonstrating dipole-induced rectification of photoinduced hole transfer (Angew. Chem. Int. Ed. 2018, 57, 12365-12369). This field susceptibility extends to the optical properties of DPPs, providing an extra dimension in their utility for photonics and optoelectronics. DPPs, and pyrrolopyrroles in general, are built on small bicyclic scaffolds, i.e., considerably smaller than those of other multi-pyrrole chromophores. The small size enhances the susceptibility of their redox properties to solvation and makes them attractive photoprobes. Therefore, this class of compounds have become indispensable agents for electrochemical and photonic science and engineering.

A new platform for the synthesis of diketopyrrolopyrrole derivatives via nucleophilic aromatic substitution reactions.

Diketopyrrolopyrroles (DPPs) are a versatile group of dyes and pigments with valuable optoelectronic properties. In this work we report the synthesis of highly fluorescent DPP derivatives through straightforward nucleophilic aromatic substitution reactions with thiols and phenols. These nucleophilic substitutions occur at room temperature and manifest a remarkable selectivity for the 4-position of the pentafluorophenyl groups. Both symmetrical (disubstitution) and non-symmetrical (monosubstitution) DPP derivatives are formed in excellent overall yields. The optical properties of the newly synthesized compounds are also discussed. The new platform may be useful for bioorthogonal chemistry.

Four Slip-Stacked Arrangements, Three Types of Photophysics: Crystal Structure and Solid-State Fluorescence of 3,6-Diaryl Substituted Furo[3,4-c]furanone Polymorphs and Regioisomers.

Six symmetrical 3,6-diaryl (aryl=phenyl, 2-, 3- and 4-tolyl, 2,4- and 3,5-xylyl) substituted furo[3,4-c]furanones (DFF) were synthesized. The computational analysis, based on density functional theory, found eight possible centrosymmetrical slipped π-stack arrangements, formed according to electron repulsion minimization principle, as for previously reported for π-isoelectronic diketopyrrolopyrroles (DPP). One of these slipped stack arrangements was found to form infinite columns in the crystals of a new polymorph of parent phenyl derivative (with centre-to-centre distance CC=6.975 Å), other three types of stacks were found for 3-tolyl (CC=6.153 Å), 4-tolyl (CC=3.849 Å) and 2,4-xylyl (CC=4.856 Å) derivatives by single crystal X-ray diffractometry. All six derivatives show intense solution fluorescence in blue/green region, with a maximum driven entirely by a number and position of methyl substituents on phenyl rings. On the other hand, the solid-state fluorescence from yellow over orange to red is observed only for four derivatives and its presence/absence, spectral position and vibronic structure is driven exclusively by the slips in π-stacks (with interplanar distance always less than 3.5 Å) of almost planar DFF molecules, resulting in J-type emission, H-type excimer-like emission and H-type quenching.

One-Pot Synthesis and Excited-State Dynamics of Null Exciton-Coupled Diketopyrrolopyrroles Oligo-Grids.

Exciton coupling in molecular aggregates plays a vital role in impacting and fine-tuning optoelectronic materials and their efficiencies in devices. A versatile platform to decipher aggregation-property relationships is built around multichromophoric architectures. Here, a series of cyclic diketopyrrolopyrrole (DPP) oligomers featuring nanoscale gridarene structures and rigid bifluorenyl spacers are designed and synthesized via one-pot Friedel-Crafts reaction. DPP dimer [2]Grid and trimer [3]Grid, which are cyclic rigid nanoarchitectures of rather different sizes, are further characterized via steady-state and time-resolved absorption and fluorescence spectroscopies. They exhibit monomer-like spectroscopic signatures in the steady-state measurements, from which null exciton couplings are derived. Moreover, in an apolar solvent, high fluorescence quantum yields and excited-state dynamics that resembled DPP monomer are gathered. In a polar solvent, the localized singlet excited state on a single DPP dissociates into the adjacent null coupling DPP with charge transfer characteristics. This pathway facilitates the evolution ofthe symmetry-broken charge-separated state (SB-CS). Notable is the fact that the SB-CS of [2]Grid is, on one hand, in equilibrium with the singlet excited state and promotes, on the other hand, the formation of the triplet excited state with a yield of 32% via charge recombination.

Determining nanoform similarity via assessment of surface reactivity by abiotic and in vitro assays

Grouping of substances is a method used to streamline hazard and risk assessment. Assessment of similarity provides the scientific evidence needed for formation of groups. This work reports on justification of grouping of nanoforms (NFs) via similarity of their surface reactivity. Four reactivity assays were used for concentration dependent detection of reactive oxygen species (ROS) generated by NFs: abiotic assays FRAS, EPR and DCFH2-DA, as well as the in vitro assay of NRF2/ARE responsive luciferase reporter activation in the HEK293 cell line. Representative materials (CuO, Mn2O3, BaSO4, CeO2 and ZnO) and three case studies of each several NFs of iron oxides, Diketopyrrolopyrroles (DPP)-based organic pigments and silicas were assessed. A novel similarity assessment algorithm was applied to quantify similarities between pairs of NFs, in a four-step workflow on concentration-response curves, individual concentration and response ranges, and finally the representative materials. We found this algorithm to be applicable to all abiotic and in vitro assays that were tested. Justification of grouping must include the increased potency of smaller particles via the scaling of effects with specific surface, and hence quantitative similarity analysis was performed on concentration-response in mass-metrics. CuO and BaSO4 were the most and least reactive representative materials respectively, and all assays found BaSO4/CuO not similar, as confirmed by their different NOAECs of in vivo studies. However, similarity outcomes from different reactivity assays were not always in agreement, highlighting the need to generate data by one assay for the representative materials and the candidate group of NFs. Despite low similarity scores in vitro some pairs of case study NFs can be accepted as sufficiently similar because the in vivo NOAECs are similar, highlighting the conservative assessment by the abiotic assays.

Hydrogen-bonded dimers of mono-alkylated diketopyrrolopyrroles and their physical properties

Judicious utilization of hydrogen bonding in diketopyrrolopyrroles (DPPs) could allow smooth carrier transfer when applied to organic semiconducting materials. In this study, we determined the association constants of dimerization by hydrogen bonding for a mono-alkylated DPP in the solution state to obtain basic insights that could aid in the utilization of hydrogen bonding. The IR spectroscopy, thermal analysis, and X-ray diffractometry results demonstrate that the hydrogen-bonded dimer structure was preferentially formed in the solid state. Electron transporting properties was only observed in the DPP derivatives, forming the hydrogen-bonded dimer structure, indicating the formation of a film morphology suitable for carrier-transport pathway.

Inside Cover: New Synthetic Approaches to N‐Aryl and π‐Expanded Diketopyrrolopyrroles as New Building Blocks for Organic Optoelectronic Materials (Angew. Chem. Int. Ed. 19/2021)

Diketopyrrolopyrroles (DPPs) are widely used as building blocks for organic optoelectronic materials. In their Research Article on page 10700, Deqing Zhang and co-workers report a new synthetic method toward both N-aryl DPPs and π-expanded DPPs. These new DPP molecules show promising light-emitting and semiconducting properties, demonstrating their usefulness for the development of high-performance organic optoelectronic materials.

Synthesis and Electronic Properties of Diketopyrrolopyrrole-Based Polymers with and without Ring-Fusion.

Diketopyrrolopyrroles (DPP) have been recognized as a promising acceptor unit for construction of semiconducting donor–acceptor (D–A) polymers, which are typically flanked by spacers such as thiophene rings via a carbon–carbon single bond formation. It may suffer from a decrease in the coplanarity of the molecules especially when bulky side chains are installed. In this work, the two N atoms in the DPP unit are further fused with C-3 of the two flanking thiophene rings, yielding a π-expanded, very planar fused-ring building block (DPPFu). A novel DPPFu-based D–A copolymer (PBDTT-DPPFu) was successfully synthesized, consisting of a benzo[1,2-b:4,5-b′]dithiophene (BDTT) unit as a donor and a DPPFu unit as an acceptor. For comparison, the unfused DPP-based counterpart PBDTT-DPP was also synthesized. Two dodecyl alkyl chains were attached to thiophene rings of DPP moieties to ensure good solubility of the DPPFu-based polymer. The influence of the ring-fusion effect on their structure, photophysical properties, electronic properties, molecular packing, and charge transport properties is investigated. Ring-fusion enhances the intermolecular interactions of PBDTT-DPPFu polymer chains as indicated by density functional theory calculation and analysis of electrostatic potential and van der Waals potential and results in significantly improved molecular packing for both the in-plane and out-of-plane directions as suggested by X-ray measurements. Finally, we correlate the molecular packing to the device performance by fabricating field-effect transistors based on these two polymers. The charge carrier mobility of the ring-fused polymer PBDTT-DPPFu is significantly higher as compared to the PBDTT-DPP polymer without ring-fusion, although PBDTT-DPPFu exhibited a much lower number-average molecular weight of 17 kDa as compared to PBDTT-DPP with a molecular weight of 108 kDa. The results from our comparative study provide a robust way to increase the interchain interaction by ring-fusion-promoted coplanarity.

Efficient charge-transfer from diketopyrrolopyrroles to single-walled carbon nanotubes.

In this contribution, the excited state charge-transfer interactions between single-walled carbon nanotubes (SWCNTs) and a variety of phenyl, 4-bromophenyl, and thiophene substituted diketopyrrolopyrroles (DPPs), is described. Atomic force microscopy (AFM) and aberration corrected high resolution transmission electron microscopy (AC-HRTEM) corroborated the successful formation of DPP/SWCNTs. Steady-state absorption, fluorescence, and Raman spectroscopies all gave insights into the impact on their ground and excited states as well as on the nature of their electronic communication/interaction. Of great value was time-resolved transient absorption spectroscopy on the femto- and nanosecond time-scales; it assisted in deciphering the charge-transfer mechanism from the DPPs to the SWCNT and in analyzing the dynamics thereof with transfer efficiencies of up to 81%. Important confirmation for the one-electron oxidized DPPs came from pulse radiolysis assays with focus on establishing their spectral fingerprints. Our full-fledged work demonstrates that the successful preparation of stable DPP/SWCNTs represents an important step towards establishing them as a viable alternative to porphyrin-based systems in emerging applications such as solar energy conversion.

Acceptor–acceptor-type conjugated polymer for use in n-type organic thin-film transistors and thermoelectric devices

The development of n -type conjugated polymers (CPs) forming an acceptor–acceptor (A–A)-type structure are quite challenging due to the synthetic limitation of imposing a functional group on the electron deficient aromatic structure. The diketopyrrolopyrroles (DPP) structure exhibits n -type characteristics; however, the extended π-structure enables stannylation at the terminal position. The stannylated DPP is beneficial for making n -type CPs, but its use in the development of n -type CPs and their application in n -type organic thin-film transistors and organic thermoelectric devices have been not extensively studied. In the present study, we synthesized the A–A-type conjugated polymer, poly [((2,5-bis(2-ethylhexyl)-3,6-di(thiophen-2-yl)-2,5-dihydropyrrolo [3,4- c ]pyrrole-1,4-dione)-5,5′-diyl)- alt -((2,7-bis(2-ethylhexyl)benzo [lmn] [3,8]phenanthroline-1,3,6,8(2 H ,7 H )-tetraone)-4,9-diyl))] (PDPP-NDI), by Stille coupling of distannylated DPP and dibrominated naphthalene diimide (NDI). The alternating copolymerization of DPP and NDI moieties led to a low-lying LUMO energy level of −4.4 eV, suitable for electron transport. The n -type organic thin-film transistors were fabricated with PDPP–NDI, and a substantial average electron mobility of 3.78 × 10 −2 cm 2 V −1 s −1 was obtained after thermal annealing. The n -type organic thermoelectric devices were developed via n -doping, and PDPP–NDI exhibited n -type thermoelectric properties, with an average power factor of 1.82 × 10 −3 μW m −1 K −2 . • An acceptor–acceptor-structured n -type alternating copolymer, PDPP–NDI, was developed. • A small bandgap of 1.03 eV and deep LUMO energy level of −4.4 eV were achieved. • The n -type characteristics of PDPP–NDI were successfully utilized in n -type OTFTs and OTE devices. • The device characteristics of both OTFT and OTE devices were fully studied and discussed.

How To Make Nitroaromatic Compounds Glow: Next-Generation Large X-Shaped, Centrosymmetric Diketopyrrolopyrroles.

Red‐emissive π‐expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three‐step strategy involving the preparation of diketopyrrolopyrrole followed by N‐arylation and subsequent intramolecular palladium‐catalyzed direct arylation. Comprehensive spectroscopic assays combined with first‐principles calculations corroborated that both N‐arylated and fused DPPs reach a locally excited (S1) state after excitation, followed by internal conversion to states with solvent and structural relaxation, before eventually undergoing intersystem crossing. Only the structurally relaxed state is fluorescent, with lifetimes in the range of several nanoseconds and tens of picoseconds in nonpolar and polar solvents, respectively. The lifetimes correlate with the fluorescence quantum yields, which range from 6 % to 88 % in nonpolar solvents and from 0.4 % and 3.2 % in polar solvents. A very inefficient (T1) population is responsible for fluorescence quantum yields as high as 88 % for the fully fused DPP in polar solvents.

How To Make Nitroaromatic Compounds Glow: Next‐Generation Large X‐Shaped, Centrosymmetric Diketopyrrolopyrroles

AbstractRed‐emissive π‐expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three‐step strategy involving the preparation of diketopyrrolopyrrole followed by N‐arylation and subsequent intramolecular palladium‐catalyzed direct arylation. Comprehensive spectroscopic assays combined with first‐principles calculations corroborated that both N‐arylated and fused DPPs reach a locally excited (S1) state after excitation, followed by internal conversion to states with solvent and structural relaxation, before eventually undergoing intersystem crossing. Only the structurally relaxed state is fluorescent, with lifetimes in the range of several nanoseconds and tens of picoseconds in nonpolar and polar solvents, respectively. The lifetimes correlate with the fluorescence quantum yields, which range from 6 % to 88 % in nonpolar solvents and from 0.4 % and 3.2 % in polar solvents. A very inefficient (T1) population is responsible for fluorescence quantum yields as high as 88 % for the fully fused DPP in polar solvents.

Multi-Stimuli-Responsive Field-Effect Transistor with Conjugated Polymer Entailing Spiropyran in the Side Chains

Multi-stimuli-responsive field-effect transistors (FETs) with organic/polymeric semiconductors have received increasing attention. Herein, we report a novel strategy for fabricating multi-stimuli-r...

Self-Assembled Extended π-Systems for Sensing and Security Applications.

Molecules and materials derived from self-assembled extended π-systems have strong and reversible optical properties, which can be modulated with external stimuli such as temperature, mechanical stress, ions, the polarity of the medium, and so on. In many cases, absorption and emission responses of self-assembled supramolecular π-systems are manifested several times higher when compared with the individual molecular building blocks. These properties of molecular assemblies encourage scientists to have a deeper understanding of their design to explore them for suitable optoelectronic applications. Therefore, it is important to bring in highly responsive optical features in π-systems, for which it is necessary to modify their structures by varying the conjugation length and by introducing donor-acceptor functional groups. Using noncovalent forces, π-systems can be put together to form assemblies of different shapes and sizes with varied optical band gaps through controlling intermolecular electronic interactions. In addition, using directional forces, it is possible to bring anisotropy to the self-assembled nanostructures, facilitating efficient exciton migration, resulting in the modulation of optical and electron-transport properties. In this Account, we mainly summarize our findings with optically tunable self-assemblies of extended π-systems such as p-phenylenevinylenes (PVs), p-phenyleneethynylenes (PEs), and diketopyrrolopyrroles (DPPs) as different stimuli-responsive platforms to develop sensors and security materials. We start with how PV self-assemblies and their coassemblies with appropriate electron-deficient systems can be used for the sensing of analytes in contact mode or in the vapor phase. For example, whereas the PV having electron-deficient terminal groups has high sensitivity toward trinitrotoluene (TNT) in contact mode, the supercoiled fibers formed by the coassembly of self-sorted stacks of C3-symmetrical PV and C3-symmetrical electron-deficient perylene bisimide are capable of sensing vapors of nitrobenzene and o-toluidine. The power of different functional groups in combination with PVs has been further illustrated by attaching CO2-sensitive tertiary amine moieties to a cyano-substituted PV, which allowed the bimodal detection of CO2 using fluorescence and Raman spectroscopy. Interestingly, the functionalization of PVs with terminal amide groups and chiral alkoxy side chains provided a mechanochromic system that allows self-erasable imaging. Whereas PVs exhibit quenching of fluorescence in most cases during self-assembly, PE derivatives exhibit aggregation-induced emission. This property of PEs has been exploited for the development of stimuli-responsive security materials, especially for currency and documents. For instance, the blue fluorescence of a PE attached to hydrophilic oxyethylene side chains coated on a filter paper upon contact with water changes to cyan emission due to the change in the molecular packing. Interestingly, the molecular packing of a Bodipy-attached PE-based gelator allowed a stress-induced change in the emission behavior, resulting in strong near-infrared (NIR) emission upon the application of mechanical stress or gelation. Finally, the use of DPP-based π-systems for the development of NIR transparent optical filters that block UV-vis light and their security- and forensic-related applications are described. These selected examples of the π-system self-assemblies provide an idea of the current status and future opportunities for scientists interested in this field of self-assembly and soft materials research.

Molecular insights and concepts to engineer singlet fission energy conversion devices

In thisReview, we showcase the fundamental processes of intermolecular and intramolecular singlet fission (SF).

Improved crystallinity of the asymmetrical diketopyrrolopyrrole derivatives by the adamantane substitution

Alkylation of diketopyrrolopyrroles (DPPs) is a powerful tool for increasing the solubility and processability of these pigments. Moreover, alkylation contributes to solid state packing and structural ordering of DPPs. In this study, the influence of the alkylation and solubilization side group engineering to DPPs on the thermal and optical properties was systematically investigated. Two series (each containing 3 derivatives: N,N'-, N,O′- and O,O′-substituted examples) of alkylated DPPs by 2-ethylhexyl and ethyladamantyl substituents were synthesized. Separation of all formed DPP derivatives was accomplished in order to perform an in-depth study of their physicochemical properties. DSC measurements revealed that the O-substitution caused a decrease in the thermal stability of DPP derivatives. On the contrary, an ethyladamantyl side chain, as a rigid alicyclic substituent, contributed very effectively to the increase of the melting point and thermal stability. The new results provide insights into the development of DPP-alkylated regioisomers and their thermal and optical properties.

π-Extended Polyaromatic Hydrocarbons by Sustainable Alkyne Annulations through Double C-H/N-H Activation.

The widespread applications of substituted diketopyrrolopyrroles (DPPs) call for the development of efficient methods for their modular assembly. Herein, we present a π‐expansion strategy for polyaromatic hydrocarbons (PAHs) by C−H activation in a sustainable fashion. Thus, twofold C−H/N‐H activations were accomplished by versatile ruthenium(II)carboxylate catalysis, providing step‐economical access to diversely decorated fluorogenic DPPs that was merged with late‐stage palladium‐catalyzed C−H arylation on the thus‐assembled DPP motif.

Role of H-Optimization in the Computed Intermolecular Interactions and Charge-Transfer Integrals in Diketopyrrolopyrroles.

Small organic conjugated systems displaying one-dimensional stacking motifs in the solid state that facilitate charge propagation are highly desirable. Noncovalent interactions, although weak, can synergistically provide those supramolecular architectures with large binding energies and associated thermal integrity. Amongst the plethora of intermolecular interactions contributing toward the overall lattice energy and stability of the charge-propagation supramolecular architectures, H-bonding interactions are well-known to play a pivotal role. Despite their critical contribution, the positions of hydrogen atoms in X-ray crystallographic data are parameterized, which can lead to significant changes in the computed intermolecular interactions. Herein, we report for the first time an analysis of the role that the optimization of the H atoms in X-ray structures has in the computed intermolecular interactions energies in diketopyrrolopyrroles (DPPs). A large dataset comprising 94 dimer pairs from 19 different DPP-based systems, including three pigment analogues, was employed. In total, more than 1400 H-X chemical bonds were considered and optimized using the M06-2X density functional at the 6-311G(d) level. Intermolecular interactions were computed for the H-optimized geometries and compared to those from nonoptimized counterparts. We report that in 35 out of the 94 dimer pairs investigated (37%), the computed intermolecular interactions were at least 2.5 kJ mol-1 larger on progression to the H-optimized geometries. In turn, lower computed values were yielded upon H-optimization computed for 8 out of the 94 dimer pairs (8%), with one case exhibiting a difference greater than 2.5 kJ mol-1. In line with the negligible changes to electron density and wavefunction overlap, the computed changes on the transfer integrals for the hole and electron were always lower than 1 kJ mol-1. The observed changes to computed intermolecular interactions can play a critical role in determining the thermal integrity of the supramolecular structures and charge propagation channels, and thus in the absence of neutron diffraction data, H atoms should be optimized prior to computation. We envisage that the results herein will be of interest to the extensive scientific community devoted to the understanding of intermolecular interactions in organic conjugated systems and the realization of superior charge-transfer-mediating materials, and given the plethora of intermolecular interactions investigated, the results are not solely limited to DPP-based architectures.

Tunable Emission from Triplet Fusion Upconversion in Diketopyrrolopyrroles.

Optical upconversion based on triplet fusion (TF), also known as triplet-triplet annihilation, is a process by which two or more low-energy photons are converted to one higher energy photon. This process requires two components, a sensitizer which absorbs the incident low-energy photons and an annihilator which emits the higher energy photons. While much attention has been given to the investigation of new types of sensitizers, very little work has been done on the exploration of new annihilators. In this work, we show that the singlet energy of diketopyrrolopyrroles (DPPs) can be altered by modifying the pendant aryl substituents to the core. This allows us to meet the energetic requirements necessary for TF upconversion and demonstrates DPPs as a new class of annihilator molecules. Using this new DPP platform, the output wavelength from upconversion can easily be tuned, which will greatly diversify the number of applications of DPPs in upconversion technologies.