Diketopyrrolopyrrole Derivatives Research Articles

Photophysical properties of donor (D)-acceptor (A)-donor (D) diketopyrrolopyrrole (A) systems as donors for applications to organic electronic devices.

Fourteen substituted diketopyrrolopyrrole (DPP) molecules in a donor (D)-acceptor (DPP)-donor (D) arrangement were designed. We employed density functional theory, time-dependent DFT, DFT-MRCI and the ab initio wave function second-order algebraic diagrammatic construction (ADC(2)) methods to investigate theoretically these systems. The examined aromatic substituents have one, two, or three hetero- and non-hetero rings. We comprehensively investigated their optical, electronic, and charge transport properties to evaluate potential applications in organic electronic devices. We found that the donor substituents based on one, two, or three aromatic rings bonded to the DPP core can improve the efficiency of an organic solar cell by fine-tuning the highest occupied molecular orbital/lowest unoccupied molecular orbital levels to match acceptors in typical bulk heterojunctions acceptors. Several properties of interest for organic photovoltaic devices were computed. We show that the investigated molecules are promising for applications as donor materials when combined with typical acceptors in bulk heterojunctions because they have appreciable energy conversion efficiencies resulting from their low ionization potentials and high electron affinities. This scenario allows a more effective charge separation and reduces the recombination rates. A comprehensive charge transfer analysis shows that D-A (DDP)-D systems have significant intramolecular charge transfer, further confirming their promise as candidates for donor materials in solar cells. The significant photophysical properties of DPP derivatives, including the high fluorescence emission, also allow these materials to be used in organic light-emitting diodes.

Impact of the spatial structure of alkyl chains on properties of thiophene-substituted diketopyrrolopyrroles: Part II – Spectroscopic study

The study concerns the impact of a difference in geometry of the side alkyl chains of oligothiophene derivatives of diketopyrrolopyrrole (DPP) on their spectroscopic properties and aggregation in solutions, in Langmuir layers, and thin films. Using a combination of theoretical and experimental approaches, this study aims to explain the aggregating behaviour of thiophene-substituted DPP derivatives. Various methods were used to characterise the dyes, including absorption spectroscopy also with polarized light, fluorescence spectroscopy, Langmuir techniques, and time-dependent density functional theory (TD-DFT) calculations. The presented results emphasise a significant impact of side alkyl chains on DPP's molecular behaviour, notably evident in thin-layer structures. Interestingly, the deconvolution of the absorption spectra revealed three bands in the red region. Insightful analysis of temperature-dependent absorption, excitation, and emission fluorescence spectra indicates the co-existence of monomer, dimer, and a higher aggregate forms, most likely a tetrameric structures. Moreover, such a complexity of molecular organisation of dyes appears already in the solution. Differences in spectral properties of the dyes studied are robustly visible in changes in the spectra of the air–water interface, where the dye with the branched side group changes the mutual orientation in dimeric structures, leading to the formation of H-type aggregates, which was observed as an almost 20-nm spectral blue shift during Langmuir layer compression. The results presented highlight the need for care in interpretation of the intensity ratio of DPP spectra and spectral shift as the sole determinants of the aggregation state.

Asymmetrical Diketopyrrolopyrrole Derivatives with Improved Solubility and Balanced Charge Transport Properties.

The diketopyrrolopyrrole (DPP) unit represents one of the building blocks more widely employed in the field of organic electronics; in most of the reported DPP-based small molecules, this unit represents the electron acceptor core symmetrically coupled to donor moieties, and the solubility is guaranteed by functionalizing lactamic nitrogens with long and branched alkyl tails. In this paper, we explored the possibility of modulating the solubility by realizing asymmetric DPP derivatives, where the molecular structure is extended in just one direction. Four novel derivatives have been prepared, characterized by a common dithyenil-DPP fragment and functionalized on one side by a thiophene unit linked to different auxiliary electron acceptor groups. As compared to previously reported symmetric analogs, the novel dyes showed an increased solubility in chloroform and proved to be soluble in THF as well. The novel dyes underwent a thorough optical and electrochemical characterization. Electronic properties were studied at the DFT levels. All the dyes were used as active layers in organic field effect transistors, showing balanced charge transport properties.

Photophysics of Benzoxazole and Dicyano Functionalised Diketopyrrolopyrrole Derivatives: Insights into Ultrafast Processes and the Triplet State.

Diketopyrrolopyrrole (DPP) functionalised with an electron donating unit acts as a donor-acceptor molecules that have shown potential for application in dyes and photovoltaics. These molecules offer broad absorption/emission properties and structure-dependent dynamics. In this study, we used femtosecond pump-probe spectroscopy to investigate the photo-initiated dynamics of thiophene linked DPP derivatives. The thio-DPPs are further functionalised by different electrons withdrawing terminal groups, namely benzoxazole and thiophene dicyanide. The benzoxazole derivative is strongly emissive and directly relaxes directly to the ground state chloroform solution. Thiophene dicyanide derivative exhibits distinct spectral evolution in the first 10 ps, associated with structural and vibronic process. Later, it crosses over to the triplet state with a yield of 20 %. In the solid-state (thin film), we observed a signal that resembles singlet fission. However, upon careful analysis of temperature-dependent steady state absorbance spectra, we conclude that these features are due to laser-induced thermal artifacts. We describe a simplified excited state evolution in the thin film that does not include any additional excited states. These findings have significant implications for the analysis of triplet formation, which plays a major role in the photophysics of many organic materials.

Urea-Comprising Single Core Diketopyrrolopyrrole Derivatives: Exploring the Synthesis, Self-Assembly and Charge Transport Properties.

Supramolecular electronics exploits the distinctive features stemming from noncovalent interactions, guiding the self-assembly of molecules to craft materials endowed with customized electronic functionalities. Hydrogen-bonded materials, characterized by their capacity to establish dynamic and stable networks, introduce an extra dimension to the development of supramolecular electronic systems. This study presents a comparative analysis of two remarkably small semiconductors utilizing diketopyrrolopyrrole functionalized with urea units as hydrogen-bonding motifs, strategically positioned at opposing ends of the conjugated core. We show how the subtle distinction in functionalization not only influences morphology and self-assembly dynamics via hydrogen-bonding and π-π stacking formation, but also holds significant consequences for ultimate charge transport properties. Our observations into the interplay of noncovalent interactions provide valuable insights and strategic pathways for the design of novel materials with enhanced electronic characteristics.

Effect of aromatic substituents on the H-bonded assembly of diketopyrrolopyrroles at solid-liquid interfaces.

Hydrogen-bonded (H-bonded) self-assembly is a suitable approach for tailoring the solid-state packing and properties of organic semiconductors. Here we studied the H-bonded self-assembly of an important class of organic semiconductors, diketopyrrolopyrrole (DPP) derivatives, diselenophenylDPP (DSeDPP), dithiazolylDPP (DTzDPP), and dithienothiophenylDPP (DTTDPP), at solid-liquid interfaces using scanning tunneling microscopy (STM) and density functional theory (DFT). At the 1-octanoic acid/highly ordered pyrolytic graphite (HOPG) interface, DSeDPP and DTzDPP either co-assemble with the solvent via H-bonding between lactam and carboxyl groups or form homoassemblies through H-bonding between the lactam groups. However, DTTDPP forms two different homoassemblies involving H-bonding between lactam groups or weak H-bonding between the lactam group and the heteroaromatic ring. Enthalpic factors for the formation of homoassemblies and co-assemblies are investigated by evaluating the inter- and intramolecular interactions in the self-assembled lattices using DFT. A homoassembly with a twisted geometry of molecules with intermolecular π-interactions is only observed for DSeDPP. The absence of homoassembly with the twisted geometry of DTzDPP is attributed to the higher strain energy required to acquire out-of-plane twists in this molecule. Our study shows the profound effects aromatic substituents can impart in the supramolecular assembly of DPP molecules, which influences film morphology and hence its properties (e.g. charge transport).

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.

Toward Silicon‐Matched Singlet Fission: Energy‐Level Modifications Through Steric Twisting of Organic Semiconductors

AbstractSinglet fission (SF) is a potential avenue for augmenting the performance of silicon photovoltaics, but the scarcity of SF materials energy‐matched to silicon represents a barrier to the commercial realization of this technology. In this work, a molecular engineering approach is described to increase the energy of the S1 and T1 energy levels of diketopyrrolopyrrole derivatives such that the energy‐level requirements for exothermic SF and energy‐transfer to silicon are met. Time‐resolved photoluminescence studies show that the silicon‐matched materials are SF active in the solid state, forming a correlated triplet pair 1(TT) – a crucial intermediate in the SF process – as observed through Herzberg‐Teller emission from 1(TT) at both 77 K and room temperature. Transient electron paramagnetic resonance studies show that the correlated triplet pair does not readily separate into the unbound triplets, which is a requirement for energy harvesting by silicon. The fact that the triplet pair do not separate into free triplets is attributed to the intermolecular crystal packing within the thin films. Nevertheless, these results demonstrate a promising route for energy‐tuning silicon‐matched SF materials.

A-A Strategy Enables Desirable Performance of All-Polymer Solar Cells Fabricated with Nonhalogenated Solvents.

Most polymer acceptors have been designed by applying a D (electron-rich unit)-A (electron-deficient unit) strategy, which are principally processed with halogenated solvents to fabricate all-polymer solar cells (all-PSCs). Two novel polymer acceptors, containing an A-A type backbone, were designed and synthesized, which can be readily dissolved in o-xylene. The polymer PY-FBTA, comprising a Y6 derivative as the first A unit and a benzotriazole derivative as the second A unit, shows smaller dihedral angles in the backbone, stronger molecular interactions, higher LUMO level, more complementary absorption spectrum, and better morphology with PM6 than the polymer PY-DPP comprising a diketopyrrolopyrrole derivative as the second A unit. Accordingly, the PM6:PY-FBTA all-PSC achieves a higher PCE of 13.95% than the all-PSC based on PM6:PY-DPP (9.51%) for thoroughly improved Jsc (22.34 mA cm-2), Voc (0.963 V), and FF (64.84%) values, which are fabricated with o-xylene as the solvent. This work demonstrates that the A-A structure is a desirable strategy for designing polymer acceptors for efficient all-PSCs prepared with nonhalogenated solvents.

Structural Study of Diketopyrrolopyrrole Derivative Thin Films: Influence of Deposition Method, Substrate Surface, and Aging.

We report the morphology and microstructure of n-dialkyl side-chain-substituted thiophene DPP end-capped with phenyl groups (Ph-TDPP-Ph) thin films and compare the influence of deposition method and substrate surface using thermally oxidized Si and graphene substrates as well as monolayer graphene surfaces with an underlying self-assembled octadecyltrichlorosilane monolayer, complemented by an aging study of spin-coated films over a 2 weeks aging period. A distinct difference in morphology was observed between spin-coated and vacuum-deposited thin films, which formed a fiber-like morphology and a continuous layer of terraced grains, respectively. After an initial film evolution, all combinations of deposition method and substrate type result in well-ordered thin films with almost identical crystalline phases with slight variations in crystallinity and mosaicity. These findings point toward strong intermolecular forces dominating during growth, and the templating effect observed for other oligomer films formed on graphene is consequently ineffective for this material type. Upon aging of spin-coated films, a noticeable evolution involving two different morphologies and crystalline phases were observed. After several days, the thin film evolved into a more stable crystal phase and a fiber-like morphology. Moreover, slight variation in optical spectra were elucidated on the basis on density functional theory calculations. These results demonstrate that thin-film properties of DPP derivatives can be tailored by manipulating the film formation process.

Alternative Functionalization of Hydrogen‐Bonded Diketopyrrolopyrrole Derivatives**

AbstractDiketopyrrolopyrrole (DPP) derivatives with thiophene capping rings are widely used as semiconductors in organic electronics. Their optoelectronic properties can be adjusted by adding different electroactive groups or by extending the conjugation of the central core, as well as by regulating their self‐assembly through noncovalent interactions. One effective strategy demonstrated to improve the performance and morphology of organic solar cells is incorporating hydrogen‐bonding units into DPPs. While the functionalization of the DPP lactams and the coupling of aromatic units to the thiophene rings are the most common procedures to tune the properties of such derivatives, modifying the thiophene capping units with hydrogen‐bonding groups is a challenging synthetic task. Despite this difficulty, incorporating amide‐containing substituents into the thiophene rings of single core thiophene‐capped DPP derivatives could yield exciting results, as the advantages of having hydrogen‐bonded π‐conjugated systems based on these modified DPPs have not been explored thoroughly. This work reports on an efficient method for synthesizing such derivatives.

Anion-π Interaction in a Diketopyrrolopyrrole Derivative.

In this work, an N-substituted diketopyrrolopyrrole (DPP) derivative Ph-DPP was synthesized, showing interaction toward Lewis alkaline anions such as F-. The typical electron-transfer-dominated anion-π interaction product Ph-DPP•- and unexpected isomer product i-Ph-DPP were both observed, and their formation mechanism was studied by density functional theory calculations, suggesting that a deprotonation initiation route is favored, which gives interesting insight for understanding the debatable role of F- in such non-covalent intermolecular interactions.

Dual-Targeting Biomimetic Nanomaterials for Photo-/Chemo-/Antiangiogenic Synergistic Therapy.

Avoiding the low specificity of phototheranostic reagents at the tumor site is a major challenge in cancer phototherapy. Meanwhile, angiogenesis in the tumor is not only the premise of tumor occurrence but also the basis of tumor growth, invasion, and metastasis, making it an ideal strategy for tumor therapy. Herein, biomimetic cancer cell membrane-coated nanodrugs (mBPP NPs) have been prepared by integrating (i) homotypic cancer cell membranes for evading immune cell phagocytosis to increase drug accumulation, (ii) protocatechuic acid for tumor vascular targeting along with chemotherapy effect, and (iii) near-infrared phototherapeutic agent diketopyrrolopyrrole derivative for photodynamic/photothermal synergetic therapy. The mBPP NPs exhibit high biocompatibility, superb phototoxicity, excellent antiangiogenic ability, and double-trigging cancer cell apoptosis in vitro. More significantly, mBPP NPs could specifically bind to tumor cells and vasculature after intravenous injection, inducing fluorescence and photothermal imaging-guided tumor ablation without recurrence and side effects in vivo. The biomimetic mBPP NPs could cause drug accumulation at the tumor site, inhibit tumor neovascularization, and improve phototherapy efficiency, providing a novel avenue for cancer treatment.

Recent Advances of Diketopyrrolopyrrole Derivatives in Cancer Therapy and Imaging Applications.

Cancer is threatening the survival of human beings all over the world. Phototherapy (including photothermal therapy (PTT) and photodynamic therapy (PDT)) and bioimaging are important tools for imaging-mediated cancer theranostics. Diketopyrrolopyrrole (DPP) dyes have received more attention due to their high thermal and photochemical stability, efficient reactive oxygen species (ROS) generation and thermal effects, easy functionalization, and tunable photophysical properties. In this review, we outline the latest achievements of DPP derivatives in cancer therapy and imaging over the past three years. DPP-based conjugated polymers and small molecules for detection, bioimaging, PTT, photoacoustic imaging (PAI)-guided PTT, and PDT/PTT combination therapy are summarized. Their design principles and chemical structures are highlighted. The outlook, challenges, and future opportunities for the development of DPP derivatives are also presented, which will give a future perspective for cancer treatment.

Unsubstituted thiophene–diketopyrrolopyrrole conjugated polymer thin films via oxidative chemical vapor deposition – electronic behavior

Chemical vapour deposition enables the polymerisation of N-unsubstituted diketopyrrolopyrrole derivative into polymer thin film combining H-bonding and conjugated covalent bonds, increasing conductivity and lifetime of electronically excited states.

Functionalized diketopyrrolopyrrole compounds for NIR-to-visible photon upconversion

Diketopyrrolopyrrole derivatives demonstrating moderate NIR-to-Vis TTA-mediated photon upconversion quantum yield (up to 3.8% out of 50%) and statistical probabilityf(up to 15.6%) are promoted as stable alternatives to a rubrene emitter.

Diketopyrrolopyrrole Derivatives as Photosensitizing Agents against Staphylococcus aureus.

Diketopyrrolopyrrole (DPP) derivatives containing sulfonamide (Sulfonamide-DPP), pyridyl (Dipyridyl-DPP) and N-methylpyridyl (MePyridyl-DPP) substituents were assessed as antibacterial photosensitizers. Non-charged DPPs showed an intense absorption band centered at about 480 nm and green fluorescence emission (ΦF ~ 0.7) in acetonitrile. The absorption of MePyridyl-DPP was bathochromically shifted at 510 nm, with decreased fluorescence emission. Sulfonamide-DPP and Dipyridyl-DPP photosensitized the formation of O2 (1 Δg ) (ΦΔ ~ 0.15-0.17), while the production induced by MePyridyl-DPP was at least 10 times lower. Furthermore, these DPPs produced a photoreduction of NBT similar to that of the control. Photodynamic inactivation induced by DPPs was first investigated at the single-bacterium level of Staphylococcus aureus attached to a surface. After 30 min irradiation, MePyridyl-DPP produced a complete eradication of the bacteria. In bacterial cell suspensions, dicationic DPP induced more than 7 log10 decrease in S. aureus cell survival after 30 min irradiation. Potentiation with iodide anions allowed a complete elimination of bacteria after 15 min therapy. This compound was also effective to eliminate S. aureus cells on biofilms. The results show that MePyridyl-DPP bearing two positive groups provides an amphiphilic character to the structure that improves the interaction with the cell envelop. This effect enhances the photocytotoxic activity of MePyridyl-DPP against bacteria.

Waterborne Paints Based on Polymeric Semiconductor for Attachable Thermoelectric Generators

Organic thermoelectric (OTE) materials offer a direct way to harvest electricity from heat resources. Although OTE paints can be coated on irregular heat sources via various solution‐processing techniques, most candidates are only soluble in toxic organic solvents and require complex preparation method, limiting their wide industrial applications. Herein, an environment‐friendly waterborne colloid based on a selenium‐substituted diketopyrrolopyrrole derivative (PDPPSe‐12) is utilized using a miniemulsion process to enable water‐dispersive OTE paints. The doped films not only exhibit prominent electrical conductivity and high Seebeck coefficient, but also show unexpected low thermal conductivity, yielding a maximum power factor and figure of merit value of up to 74.77 ± 1.76 μW m−1 K−2 and 0.14, respectively. More importantly, their application potential in a realistic thermoelectric generator (TEG) on a paper substrate by painting is demonstrated, which possesses an output power of 14.70 nW under a temperature difference of 19 K. For the first time, these results reveal that the fabrication of waterborne OTE paints can decrease the thermal conductivity and its integrated organic TEGs exhibit preferable performance. These results offer valuable insights for designing high‐performance OTE paints toward multiple‐energy supplier systems in an environmentally friendly way.

Parallel triplet formation pathways in a singlet fission material

Harvesting long-lived free triplets in high yields by utilizing organic singlet fission materials can be the cornerstone for increasing photovoltaic efficiencies potentially. However, except for polyacenes, which are the most studied systems in the singlet fission field, spin-entangled correlated triplet pairs and free triplets born through singlet fission are relatively poorly characterized. By utilizing transient absorption and photoluminescence spectroscopy in supramolecular aggregate thin films consisting of Hamilton-receptor-substituted diketopyrrolopyrrole derivatives, we show that photoexcitation gives rise to the formation of spin-0 correlated triplet pair 1(TT) from the lower Frenkel exciton state. The existence of 1(TT) is proved through faint Herzberg-Teller emission that is enabled by vibronic coupling and correlated with an artifact-free triplet-state photoinduced absorption in the near-infrared. Surprisingly, transient electron paramagnetic resonance reveals that long-lived triplets are produced through classical intersystem crossing instead of 1(TT) dissociation, with the two pathways in competition. Moreover, comparison of the triplet-formation dynamics in J-like and H-like thin films with the same energetics reveals that spin-orbit coupling mediated intersystem crossing persists in both. However, 1(TT) only forms in the J-like film, pinpointing the huge impact of intermolecular coupling geometry on singlet fission dynamics.

Singlet Fission in Colloidal Nanoparticles of Amphipathic Diketopyrrolopyrrole Derivatives: Probing the Role of the Charge Transfer State.

To evaluate the role of the charge transfer (CT) state in the singlet fission (SF) process, we prepared three 3,6-bis(thiophen-2-yl)diketopyrrolopyrrole (TDPP) derivatives with zero (Ph2TDPP), one (Ph2TDPP-COOH), and two (Ph2TDPP-(COOH)2) carboxylic groups, respectively. Their colloidal nanoparticles were also prepared by a simple precipitation method. The SF dynamics and mechanism in these colloid nanoparticles were investigated by using steady-state/transient absorption and fluorescence spectroscopy. Steady-state absorption spectra reveal that the strength of the CT resonance interactions between the adjacent DPP units is increased gradually from Ph2TDPP to Ph2TDPP-COOH and then to Ph2TDPP-(COOH)2. Fluorescence and transient absorption spectra demonstrate that SF is proceeded via a CT-assisted superexchange mechanism in these three nanoparticles. Furthermore, SF rate and yield are enhanced gradually with the increase of the number of the carboxylic group, which may be attributed to the enhancement of the CT coupling strength. The result of this work not only provides a better understanding of the SF mechanism especially for the role of the CT state but also gives some new insights for the design of efficient SF materials based on DPP derivatives.