Push-pull Molecules Research Articles

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules.

The comprehensive characterization of Intramolecular Charge Transfer (ICT) stemming in push-pull molecules with a delocalized π-system of electrons is noteworthy for a bespoke design of organic materials, spanning widespread applications from photovoltaics to nanomedicine imaging devices. Photo-induced ICT is characterized by structural reorganizations, which allows the molecule to adapt to the new electronic density distribution. Herein, we discuss recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles. We focus the discussion on femtosecond Transient Absorption Spectroscopy (TAS) enabling us to follow the transition from a Locally Excited (LE) state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms. In many cases, the charge transfer transition is accompanied by structural rearrangements, such as the twisting or molecule planarization. The possibility of an accurate prediction of the charge-transfer occurring in complex molecules and molecular materials represents an enormous advantage in guiding new molecular and materials design. We briefly report on recent advances in ultrafast multidimensional spectroscopy, in particular, Two-Dimensional Electronic Spectroscopy (2DES), in unraveling the ICT nature of push-pull molecular systems. A theoretical description at the atomistic level of photo-induced molecular transitions can predict with reasonable accuracy the properties of photoactive molecules. In this framework, the review includes a discussion on the advances from simulation and modeling, which have provided, over the years, significant information on photoexcitation, emission, charge-transport, and decay pathways. Density Functional Theory (DFT) coupled with the Time-Dependent (TD) framework can describe electronic properties and dynamics for a limited system size. More recently, Machine Learning (ML) or deep learning approaches, as well as free-energy simulations containing excited state potentials, can speed up the calculations with transferable accuracy to more complex molecules with extended system size. A perspective on combining ultrafast spectroscopy with molecular simulations is foreseen for optimizing the design of photoactive compounds with tunable properties.

Tuning the Photophysical Properties of Push-Pull Azaheterocyclic Chromophores by Protonation: A Brief Overview of a French-Spanish-Czech Project.

Conjugated push-pull molecules that incorporate nitrogen heterocycles as electron-withdrawing units are interesting materials because of their luminescence properties. These chromophores can be easily and reversibly protonated at the nitrogen atom of the heterocyclic ring and this can cause dramatic color changes. White and multi-color photoluminescence both in solution and in the solid state can be obtained by an accurate control of the amount of acid. Thus, with a suitable design these compounds have potential applications in the development of colorimetric pH sensors and the fabrication of OLEDs based on only one material. We provide here a brief overview of our collaborative efforts made in this area.

Asymmetric push-pull small molecules with auxiliary electron-accepting unit for bulk heterojunction organic solar cells

Two small molecular donors (TPA-DPP and TPA-DPP-MDN) were designed with asymmetric push-pull structure, namely, donor-acceptor (D-A) and donor-acceptor-acceptor (D-A-A) systems. They were synthesized and investigated by thermogravimetric analysis, UV–vis spectra, X-ray diffraction, density functional theory (DFT) calculation, electrochemical and the photovoltaic (PV) measurement. The D-A-A architecture (TPA-DPP-MDN) exhibited lower highest occupied molecular orbital (HOMO) of –5.18 eV, narrower optical band gap of 1.52 eV, better thermal stability and higher degree of ordered aggregation than these of the D-A system (TPA-DPP). TPA-DPP-MDN based PV device showed better performance with higher open-circuit voltage (VOC) and short-circuit current density (JSC) than these of TPA-DPP based PV devices due to the low-lying HOMO level and wide spectral absorption range of TPA-DPP-MDN.

2,3-di(2-furyl) quinoxaline bearing 3 -ethyl rhodanine and 1,3 indandione based heteroaromatic conjugated T-shaped push -pull chromophores: Design, synthesis, photophysical and non-linear optical investigations

The design, synthesis, computational, spectroscopic, and, the second and third order non-linear optical studies of a two new π-deficient cross-conjugated T-shaped push-pull molecules (QFR and QFI) consisting of 3-ethyl rhodanine and 1,3 indandione substituted with heterocyclic quinoxaline ring were synthesized by Knoevenagel condensation reaction of the precursor dialdehydes with active dye molecules were described in detail. In the as synthesized molecule, the electron donating thiophene moiety acts as an efficient π-bridge on either side to the quinoxaline core that permits good viability in fine-tuning the optical absorption spectrum with good solubility. The computational studies of these molecules show efficient intra molecular charge transfer (ICT) processes analyzed through their molecular orbital characteristics, excitation energy, absorption maxima, oscillator strength and Mulliken population analysis. The comparison study between the structures of these push-pull molecules were done by their photophysical characteristics including CIE coordinates; thermal characteristics, XRD studies and electrochemical analysis. The time-resolved fluorescence spectra with nanosecond time profile were measured to detect the delayed fluorescent performance of the push-pull molecules QFR and QFI. Hyper-Rayleigh scattering (HRS) in chloroform solution of varying concentrations, using a standard wavelength at 1064 nm was used to assess their first order hyperpolarizability. Optical non-linear property was again proved by open-aperture Z-scan technique investigated at 532 nm and the observed optical limiting behavior was originated from the reverse saturable absorption (RSA) process. The second and third order NLO studies reveals that 3-ethyl rhodanine substituted QFR molecule (β value from HRS, 84.64 × 10−30 esu and βeff from Z scan, 10 × 10−10 m/W) shows high non-linear optical properties and thermal stability compared with 1,3 indandione substituted QFI (β value from HRS, 48.00 × 10−30 esu and βeff value from Z scan, 2 × 10−10m/W).

Addressing Charge-Transfer and Locally-Excited States in a Twisted Biphenyl Push-Pull Chromophore.

We present the synthesis and spectroscopic characterization of a twisted push-pull biphenyl molecule undergoing photoinduced electron transfer. Steady-state and transient absorption spectra suggest, in this rigid molecular structure, a subtle interplay between locally-excited and charge-transfer states, whose equilibrium and dynamics is only driven by solvation. A theoretical model is presented for the solvation dynamics and, with the support of quantum chemical calculations, we demonstrate the existence of two sets of states, having either local or charge-transfer character, that only "communicate" thanks to solvation, which is the sole driving force for the charge-separation process.

Push-pull molecules bearing a hydrazonocyclopentadiene acceptor moiety: from the synthesis to organic photovoltaic applications

First representatives of a novel class of compounds containing an electron-accepting hydrazonocyclopentadiene moiety, π-conjugated phenylene spacer, and electron-donating triphenylamine moiety have been synthesized. Investigation of their optical, electrochemical and photovoltaic properties revealed a high potential of the hydrazonocyclopentadiene acceptor moiety in the design of donor-acceptor compounds for organic photovoltaics.

Molecular engineering of benzodithiophene and diketopyrrolopyrrole-contained push-pull small molecules for efficient solution-processed organic solar cells

To investigate the relationships between molecular structures and their photovoltaic performance in solar cells, molecular engineering of push-pull small molecules from D-A to A-D-π-D-A architectures is proposed here using benzodithiophene, diketopyrrolopyrrole and fluorine-substituted phenyl groups as D, A and conjugated π units, respectively. In contrast to BDT-DPP, A-D-π-D-A structured DBDT-DPP-BF not only exhibits largely improved optical properties and matched energy levels, but also displays much ordered molecular packing and balanced hole/electron mobility in transistors. Therefore, compared with the inferior photovoltaic performance for BDT-DPP (PCE = 0.29%), the maximum PCE value of 5.27% with a significantly improved Jsc value of 12.01 mA/cm2 is finally achieved in DBDT-DPP-BF-based solar cells, indicating that manipulating molecular backbone from D-A to A-D-π-D-A architectures in the benzodithiophene and diketopyrrolopyrrole-contained push-pull small molecules here is an efficient method to enhance their photovoltaic performance in solar cells.

Small isomeric push-pull chromophores based on thienothiophenes with tunable optical (non)linearities.

Fourteen new D-π-A push-pull chromophores based on two isomeric thienothiophene donors and seven acceptors of various electronic natures have been designed and conveniently synthesized. In contrast to known thienothiophene push-pull molecules, the prepared small chromophores proved to be organic materials with easily tunable thermal, electrochemical and (non)linear optical properties. It has also been shown that small structural variation may result in significantly improved/varied fundamental properties. Very detailed structure-property relationships were elucidated within the systematically developed series of push-pull molecules, which may serve as a useful guide in designing new D-π-A molecules based on fused thiophene scaffolds.

Probing Polarity and Heterogeneity of Lipid Droplets in Live Cells Using a Push-Pull Fluorophore.

Lipid droplets (LDs) are organelles composed of a lipid core surrounded by a phospholipid monolayer. Lately, LDs have attracted considerable attention due to recent studies demonstrating their role in a variety of physiological processes as well as diseases. Herein we synthesized a push-pull molecule named DAF (Dimethyl Aniline Furaldehyde) that possesses a strong positive solvatochromism in emission of 119 nm from toluene to methanol. Its impressive fluorogenic properties from water to oil (2000-fold) as well as its high quantum yields (up to 0.97) led us to investigate its ability to sense the distribution of polarity in live cells by fluorescence ratiometric imaging. When added to live cells and excited at 405 nm, DAF immediately and brightly stain lipid droplets using a blue channel (410-500 nm) and cytoplasm in a red channel (500-600 nm). DAF also proved to be compatible with fixation thus allowing 3D imaging of LDs in their cytoplasm environment. Taking advantage of DAF emission in two distinct channels, ratiometric imaging was successfully performed and led to the polarity mapping of the cell unraveling some heterogeneity in polarity within LDs of the same cell.

Thermal, spectroscopic, electrochemical, and electroluminescent characterization of malononitrile derivatives with triphenylamine structure.

Three push-pull molecules with linear, quadrupolar and tripodal arrangements, consisting of triphenylamine (electro-donor) substituted with malononitrile groups (electro-acceptor), were synthesized with high yield by a simple procedure. Impact of the number of malononitrile substituents on optoelectronic properties was investigated with cyclic voltammetry, absorption and emission spectroscopy, as well as density functional theory calculation. The derivatives formed amorphous materials and exhibited low energy band gaps ranging from 2.06 to 2.49 eV. UV-Vis absorption and photoluminescence emission spectra were investigated in solutions (CHCl3, NMP) and in solid-state as thin films and two kinds of blends (with PMMA and PVK:PBD). Quantum yield of photoluminescence was dependent on the molecule structure, solvent, and solid-state layer formulation. The compounds exhibited high photoluminescence quantum yield in the range of 15-42% and 12-59% in solid-state as film and blend with PMMA (1 wt%), respectively, being promising for applications in light emitting diodes. The diodes with active layer consisting of neat derivatives and compounds molecularly dispersed in PVK:PBD (50:50 wt%) matrix showed orange and green electroluminescence.

Photophysical and Protonation Time Resolved Studies of Donor-Acceptor Branched Systems With Pyridine Acceptors.

A comparative study of the photophysical properties of octupolar pyridyl-terminated triphenylamine molecule, with its quadrupolar and dipolar analogues, by means of ambient and low temperature steady state spectroscopy and femtosecond to nanosecond time-resolved fluorescence spectroscopy is reported. The push-pull molecules bear triphenylamine electron donating core, pyridine peripheral electron acceptors, and acetylene π-bridge. The samples were studied in solvents of varying polarity and also upon addition of small amounts of acetic acid to induce protonation of the pyridine group. All samples exhibit significant positive fluorescence solvatochromism as well as a relaxation of their excited state to a solvent relaxed intramolecular charge transfer state on the picosecond time scale. For the octupolar compound, excited state relaxation occurs simultaneously with excitation energy hopping among the branches. The hopping time is solvent polarity controlled since it becomes slower as the polarity increases. The experimental hopping times are compared to those predicted by Förster and Fermi formulations. The samples are capable of emitting broadband light covering almost the whole visible spectrum by careful control of protonation. Energy transfer from the neutral toward the protonated species on the 1 ps time scale is revealed.

Facile synthesis of bis-dicyanovinylidene-end-capped push-pull molecules as panchromatic absorbers

A new π-conjugated building block containing bis-dicyanovinylidene as an end-capping group has been explored for the development of n-type organic semiconductors. This building block can be easily obtained from commercialized 2,3-thiophenedicarboxaldehyde and introduced into a π-conjugated system in high-yield. By using indaceno[1,2-b:5,6-b']dithiophene (IDT) as the core moiety, an A-π-D-π-A molecule with up to 8 cyano-groups (DH8CN) was firstly synthesized and employed as an electron-accepting material in bulk-heterojunction organic solar cells. Preliminary organic cell fabrication gave a 1.1% power conversion efficiency with PTB7-Th and DH8CN as active layer, show the potential of this bis-dicyanovinylidene group in organic photovoltaics.

From Linear to T‐Shaped Indan‐1,3‐dione Push–Pull Molecules: A Comparative Study

A series of indan‐1,3‐dione‐based linear, quadrupolar and T‐shaped push–pull chromophores have been designed and synthesized by the Knoevenagel condensation and Pd‐catalyzed Suzuki–Miyaura or Sonogashira cross‐coupling reactions. The number and position of the peripheral donor branches attached to the central withdrawing indan‐1,3‐dione moiety have been varied jointly with the type of π‐linker used in order to modulate fundamental optoelectronic properties. The molecular structure of two chromophores has been confirmed by X‐ray analysis. The thermal and optoelectronic properties have further been investigated by differential scanning calorimetry, electrochemistry, UV/Vis absorption spectroscopy, and DFT calculations. Based on these experimental and theoretical data, thorough structure–property relationships have been further evaluated and influence of the particular structural modification on chromophore properties has been discussed.

Malononitrile derivatives as push-pull molecules: Structure - properties relationships characterization

A series of molecules with a dicyanovinyl acceptor connected with various substituted phenyls as donor blocks were synthesized and characterized. The thermal, electrochemical and photophysical properties of these compounds were investigated and compared. DSC and TGA measurements revealed that all compounds showed high both different melting transitions and the beginning of decomposition. The electrochemical studies did not show significant differences in energy band gap being between 2.41 and 2.55 eV (except for one with carbazole unit), which was also supported by the density functional theory calculations. They emitted light with higher photoluminescence quantum yield in film than in solution. Blends containing the malononitrile derivatives dispersed in a solid matrix consisting of poly(9-vinylcarbazole) and (2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole) emitted with small or high contribution from the host, signaling efficient or incomplete energy transfer from host to guest molecules. Emission of light under external voltage by diodes based on these blends was observed.

Establishing the Critical Role of Oriented Aggregation in Molecular Solid State Fluorescence Enhancement.

The general occurrence of fluorescence emission quenching in molecular aggregates is circumvented in select classes of molecules. This has largely been attributed to the rigidification of the molecule and its environment, which hinders non-radiative excited state energy loss through structural relaxation; since such an effect should in principle apply to most aggregates and crystals, there must clearly be other critical factors that make the select molecules exceptional. Discovery of three crystalline structures of a new push-pull molecule in its enantiomorphic and racemic forms, exhibiting not only very high, but distinctly different solid state fluorescence enhancements, has now allowed a systematic investigation of the role of intramolecular and intermolecular excited state energy loss pathways. Crystallographic, spectroscopic and computational investigations provide a detailed appraisal of the assembly patterns in the crystals, and rigorous establishment of an inverse correlation between intermolecular energy transfer and solid state fluorescence. The study provides a clear visualization of the critical role of oriented molecular aggregation in solid state fluorescence efficiency enhancement.

Simple donor-acceptor molecule with long exciton diffusion length for organic photovoltaics

Abstract To succeed in commercial applications, donor materials for organic solar cells should combine high stability and simple synthesis with high performance in devices. Here, we present a new small π-conjugated molecule, TPA-T-DCV-Ph, which meets those requirements. Simple and efficient three-step synthesis produces a push-pull molecule with triphenylamine donor and phenyldicyanovinyl acceptor groups, which is suitable for both solution processing and vacuum deposition. The unique property of TPA-T-DCV-Ph is an unusually long exciton diffusion length of >25 nm due to the combined effect of long exciton lifetime and surprisingly low energy disorder. This, together with a device engineering, resulted in >5% efficiency for TPA-T-DCV-Ph:C70 vacuum-processed solar cells. The results obtained are envisioned to be further improved by optimizing the absorption of the molecule and light management in the device which can push the efficiency even further.

Spectroscopic and DFT investigation on the photo-chemical properties of a push-pull chromophore: 4-Dimethylamino-4′-nitrostilbene

4-Dimethylamino-4′-nitrostilbene (DANS), a π-conjugated push-pull molecule, has been investigated by means of a combined spectroscopic and computational approach. When the Raman excitation is close to the visible electronic transition of DANS, vibrational bands not belonging to DANS appear in the spectra, increasing with the laser power. These bands are observed at room temperature in the solid phase, but not at low temperature or in solution, and we interpret them as due to a thermally-activated photoreaction occurring under laser irradiation in the visible spectral region. Density-functional calculations correctly reproducing the electronic and vibrational spectra of DANS, describe the charge-transfer process, indicate that an azo-derivative is the product of the photoreaction of DANS and provide a reasonable interpretation of this process.

Thermally induced crystallization, hole-transport, NLO and photovoltaic activity of a bis-diarylamine-based push-pull molecule

The synthesis of a molecule constituted of two diarylamine-based push-pull chromophores covalently linked via their nitrogen atom is described. Comparison of the electronic properties with the parent monomer shows that dimerization has negligible influence on the electronic properties of the molecule but exerts a dramatic impact on the capacity of the material to self-reorganize. Application of thermal annealing to thin films induces the crystallization under original morphologies, a process accompanied by a partial bleaching of the absorption in the visible range and by a huge increase of hole-mobility. X-ray diffraction data on single crystals reveal the presence of π-stacked organization with a non-centrosymmetric co-facial arrangement of the dipoles which leads to intrinsic 2nd order bulk NLO properties of thin films as evidenced by second harmonic generation under 800 nm laser light. The implications of this thermally induced crystallization on the photovoltaic properties of the material are discussed on the basis of preliminary results obtained on simple bilayer organic solar cells.

Thin-film photovoltaic devices incorporating low-bandgap push-pull molecules dispersed in passive polymeric matrices

Active layers in many thin-film organic photovoltaic devices (OPVs) contain light-absorbing polymers that serve as electron donors, mixed with appropriate electron acceptors. In principle, the polymers can be replaced by small molecules with suitable bandgaps, which offer multiple advantages, including well-defined structures and methods of synthesis and purification that provide uniform samples. However, such materials often undergo separation of phases and crystallization, so making long-lived films that remain smooth, homogeneous, flexible, and transparent is not easy. We have found that effective OPVs can be made by dispersing mixtures of low-bandgap push–pull small molecules as electron donors and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as electron acceptor in matrices of optoelectronically passive conventional polymers, including polystyrene, poly(methyl methacrylate), poly(vinyl chloride), poly(ethylene glycol), and poly(dimethylsiloxane). By varying the identity of the matrix, its molecular weight, the loading of active components, and the conditions of annealing, we have produced efficient OPVs from components that would otherwise have undergone phase separation and crystallization, leading to poor performance. Layers with up to 35% matrix were found to be effective and could be fabricated at room temperature by simple processes. To probe the role of the polymers as dispersants, morphologies of composite films were examined by atomic force microscopy and electron microscopy. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017

Triphenylamine-Based Push-Pull Molecule for Photovoltaic Applications: From Synthesis to Ultrafast Device Photophysics.

Small push–pull molecules attract much attention as prospective donor materials for organic solar cells (OSCs). By chemical engineering, it is possible to combine a number of attractive properties such as broad absorption, efficient charge separation, and vacuum and solution processabilities in a single molecule. Here we report the synthesis and early time photophysics of such a molecule, TPA-2T-DCV-Me, based on the triphenylamine (TPA) donor core and dicyanovinyl (DCV) acceptor end group connected by a thiophene bridge. Using time-resolved photoinduced absorption and photoluminescence, we demonstrate that in blends with [70]PCBM the molecule works both as an electron donor and hole acceptor, thereby allowing for two independent channels of charge generation. The charge-generation process is followed by the recombination of interfacial charge transfer states that takes place on the subnanosecond time scale as revealed by time-resolved photoluminescence and nongeminate recombination as follows from the OSC performance. Our findings demonstrate the potential of TPA-DCV-based molecules as donor materials for both solution-processed and vacuum-deposited OSCs.