Acceptor Chromophores Research Articles

σ‐Conjugation and H‐Bond‐Directed Supramolecular Self‐Assembly: Key Features for Efficient Long‐Lived Room Temperature Phosphorescent Organic Molecular Crystals

AbstractLong‐lived room temperature phosphorescence from organic molecular crystals attracts great attention. Persistent luminescence depends on the electronic properties of the molecular components, mainly π‐conjugated donor–acceptor (D‐A) chromophores, and their molecular packing. Here, a strategy is developed by designing two isomeric molecular phosphors incorporating and combining a bridge for σ‐conjugation between the D and A units and a structure‐directing unit for H‐bond‐directed supramolecular self‐assembly. Calculations highlight the critical role played by the two degrees of freedom of the σ‐conjugated bridge on the chromophore optical properties. The molecular crystals exhibit RTP quantum yields up to 20 % and lifetimes up to 520 ms. The crystal structures of the efficient phosphorescent materials establish the existence of an unprecedented well‐organization of the emitters into 2D rectangular columnar‐like supramolecular structure stabilized by intermolecular H‐bonding.

Multiple Intramolecular Charge Transfers in Multimodular Donor–Acceptor Chromophores with Large Two-Photon Absorption

New multimodular donor–acceptor chromophores combining phenothiazine (D′), benzothiadiazole (A), and diphenylamine/carbazole (D) units in complex configurations (D−π–A−π–D′−π–A−π–D and D–A−π–D′−π–A...

Indacenodithienothiophene based chromophore with cyclopentadienylidenehydrazine acceptor moieties

A novel acceptor–donor–acceptor chromophore IDTT-HC2P with an indacenodithienothiophene core linked with two hydrazinylidenecyclopentadiene terminal acceptor groups was designed and synthesized via the reaction of dilithiated indacenodithienothiophene with the corresponding diazo compound. The frontier orbital energy levels as well as the bandgap which were estimated from both optical and electrochemical properties are very closely related to those of ITIC which in turn is associated with high power conversion efficiencies.

D-π-A chromophores with a quinoxaline core in the π-bridge and bulky aryl groups in the acceptor: Synthesis, properties, and femtosecond nonlinear optical activity of the chromophore/PMMA guest-host materials

Novel D-π-A chromophores with quinoxaline/quinoxalinone core in the π-conjugated bridge and various bulky groups in the acceptor moiety have been synthesized and systematically investigated at molecular level by UV–Vis spectroscopy, DFT calculations, electrochemical and TGA-DSC methods as well as at materials level by the example of PMMA-based composite polymer materials doped with different chromophore contents using molecular modeling and SHG technique. Chromophores exhibit positive dioxane/chloroform solvatochromic shift of ca. 50 nm, high values of first hyperpolarizability and dipole moment, small energy gap and good thermal stability. Tolyl and cyclohexylphenyl substituents unlike phenyl can be treated as most effective isolating groups, preventing chromophore pronounced aggregation even at 30 wt% content. Femtosecond nonlinear optical (NLO) activity was studied for poled thin guest-host polymer films with various chromophore weight content. Film DBA-VQPhV-TCFPhCy(25 wt%)/PMMA with bulky cyclohexylphenyl groups in chromophore acceptor shows maximal NLO coefficient, d33, values among the studied materials (37 pm/V) as well as good long-term stability of NLO response together with excellent chromophore thermal stability (Td = 256 °C). Composite materials doped with quinoxaline chromophores are photostable with respect to laser pulses with peak intensities up to 11 GW/cm2.

Calculation of the Structure and Properties of Optical Nonlinear Fluorine-Containing Chromophores

Possible modifications of chromophore structures with nonlinear optical properties by bonding F atoms and F-containing groups to the acceptor site of the molecules are considered. Quantum chemical calculations of dipole moments and first hyperpolarizability were performed for several nonlinear chromophores based on N-ethyl- N-(2-hydroxyethyl)-4-phenylazoaniline and modified by the addition of F atoms and F-containing groups to the acceptor site. Positions of maxima in the electronic absorption spectrum and the Mulliken charges on the atoms are found. It is shown that addition of F atoms and F-containing groups to the chromophore acceptor site changes (increases) the efficiency parameter, defined as the product of the dipole moment and the first hyperpolarizability. The main parameters of a waveguide modulator made of an electro-optical polymer composite with F-containing chromophores embedded in it are estimated.

Monitoring the evolution of intersite and interexciton coherence in electronic excitation transfer via wave-packet interferometry.

We detail an experimental strategy for tracking the generation and time-development of electronic coherence within the singly excited manifold of an energy-transfer dimer. The technique requires that the two monomers have nonparallel electronic transition-dipole moments and that these possess fixed orientations in space. It makes use of two-dimensional wave-packet interferometry (WPI or whoopee) measurements in which the A, B, C, and D pulses have respective polarizations e, e, e, and e'. In the case of energy-transfer coupling that is weak or strong compared to electronic-nuclear interactions, it is convenient to follow the evolution of intersite or interexciton coherence, respectively. Under weak coupling, e could be perpendicular to the acceptor chromophore's transition dipole moment and the unit vector e' would be perpendicular to the donor's transition dipole. Under strong coupling, e could be perpendicular to the ground-to-excited transition dipole to the lower exciton level and e' would be perpendicular to the ground-to-excited transition dipole to the upper exciton level. If the required spatial orientation can be realized for an entire ensemble, experiments of the kind proposed could be performed by either conventional four-wave-mixing or fluorescence-detected WPI methods. Alternatively, fluorescence-detected whoopee experiments of this kind could be carried out on a single energy-transfer dimer of fixed orientation. We exhibit detailed theoretical expressions for the desired WPI signal, explain the physical origin of electronic coherence detection, and show calculated observed-coherence signals for model dimers with one, two, or three internal vibrational modes per monomer and both weak and strong energy-transfer coupling.

Light‐Harvesting Supramolecular Polymers: Energy Transfer to Various Polyaromatic Acceptors

A supramolecular light‐harvesting antenna consisting of 3,6‐disubstituted phosphodiester‐linked phenanthrene trimers (donors) was doped with different charged and uncharged polyaromatic and heteroaromatic acceptor chromophores. Excitation of the phenanthrene moieties is followed by energy transfer to the acceptor molecules and radiative relaxation. The self‐assembled fiber structure of the phenanthrene trimers is not altered by the dopant, as verified by atomic force microscopy (AFM). Among several neutral and cationic acceptor chromophores, benzo(a)pyrene emerged as one of the highest fluorescence quantum yields, reaching 31 % at a chromophore/phenanthrene ratio of 12 mol‐%. The energy transfer is probably a combination of Förster resonance energy transfer (FRET) and a coherent energy transfer mechanism.

Phosphorescence Energy Transfer: Ambient Afterglow Fluorescence from Water‐Processable and Purely Organic Dyes via Delayed Sensitization

AbstractAmbient afterglow luminescence from metal‐free organic chromophores would provide a promising alternative to the well‐explored inorganic phosphors. However, the realization of air‐stable and solution‐processable organic afterglow systems with long‐lived triplet or singlet states remains a formidable challenge. In the present study, a delayed sensitization of the singlet state of organic dyes via phosphorescence energy transfer from organic phosphors is proposed as an alternative strategy to realize “afterglow fluorescence”. This concept is demonstrated with a long‐lived phosphor as the energy donor and commercially available fluorescent dyes as the energy acceptor. Triplet‐to‐singlet Förster‐resonance energy‐transfer (TS‐FRET) between donor and acceptor chromophores, which are co‐organized in an amorphous polymer matrix, results in tuneable yellow and red afterglow from the fluorescent acceptors. Moreover, these afterglow fluorescent hybrids are highly solution‐processable and show excellent air‐stability with good quantum yields.

Phosphorescence Energy Transfer: Ambient Afterglow Fluorescence from Water-Processable and Purely Organic Dyes via Delayed Sensitization.

Ambient afterglow luminescence from metal-free organic chromophores would provide a promising alternative to the well-explored inorganic phosphors. However, the realization of air-stable and solution-processable organic afterglow systems with long-lived triplet or singlet states remains a formidable challenge. In the present study, a delayed sensitization of the singlet state of organic dyes via phosphorescence energy transfer from organic phosphors is proposed as an alternative strategy to realize "afterglow fluorescence". This concept is demonstrated with a long-lived phosphor as the energy donor and commercially available fluorescent dyes as the energy acceptor. Triplet-to-singlet Förster-resonance energy-transfer (TS-FRET) between donor and acceptor chromophores, which are co-organized in an amorphous polymer matrix, results in tuneable yellow and red afterglow from the fluorescent acceptors. Moreover, these afterglow fluorescent hybrids are highly solution-processable and show excellent air-stability with good quantum yields.

Macromolecular Effect Stabilized Color-Tunable and Room Temperature Charge-Transfer Complexes Based on Donor–Acceptor Assemblies

We report one of the first examples of room temperature stable solid-state charge transfer (CT) complexes based on a segmented π-conjugated polymer and rylene diimide donor–acceptor system having tunable optical transitions from the visible to NIR region in the solar spectrum. Semicrystalline and amorphous segmented oligo-phenylenevinylene (OPV) chromophore containing polymers were tailor-made with flexible polymethylene chains in the backbone. The electron rich segmented OPV polymers were complexed with two electron-deficient diimides based on naphthalene (NDI) and phenylene (PDI) core. The binary complexes of segmented OPV polymers and rylene diimides produced unique classes of CT complexes based on OPV-NDI and OPV-PDI chromophore diads. Electron microscope, polarizing microscope, and X-ray diffraction analyses provided direct evidence for the two-dimensional lamellar packing of D–A self-assembly in the solid state. Detailed absorption and emission photophysical studies revealed that the donor OPV polymers and acceptor chromophores exhibited a 1:1 complex with respect to the long-range order of D–A–D–A–D–A π-stacked supramolecular assemblies. The role of the macromolecular effect on the CT complexation was further investigated using structurally identical OPV monomers. The monomer OPV-NDI complexes (or PDI complexes) were found to exhibit CT complex in the solution; however, they underwent uncontrollable phase separation into their individual D and A crystalline domains and lost their CT self-assembly in the solid state. Interestingly, the macromolecular effect driven supramolecular self-organization of long chain segmented OPV polymers produced stable CT complexes both in solution and solid state under ambient conditions. Segmented OPV polymer + PDI and segmented OPV polymer + NDI complexes were produced as red and green colored CT complexes, respectively. This enabled the accomplishment of room temperature stable CT complexes in π-conjugated polymers having absorption ranging from 350 to 1100 nm. These donor–acceptor CT self-assemblies are processable into thin films under solvent free melt crystallization process; thus, the present segmented polymer design strategy opens up a platform for donor–acceptor CT complexes.

Unusual Non-Kasha Photophysical Behavior of Aggregates of Push–Pull Donor–Acceptor Chromophores

Unlike the Frenkel exciton model, the essential state model (ESM) for aggregates of donor–acceptor (DA) chromophores accounts self-consistently for the effect of the reaction field on the ground an...

Engineering pH-responsive switching of donor-π-acceptor chromophore alignments along a peptide nanotube scaffold.

A cyclic tri-β-peptide cyclo(β-Ala-β-Ala-β-Lys) having diethylaminonaphthalimide at the β-Lys side chain (CP3Npi) self-assembled into a peptide nanotube in a solution of HFIP and water. CD spectra of the CP3Npi nanotubes show a negative Cotton effect at 441 nm and a positive Cotton effect at 393 nm, indicating that D–π–A naphthalimide chromophores are aligned in a left-handed chiral way along the nanotube. The CP3Npi nanotubes bear positive charges under acidic conditions retaining the nanotube structure but pH-responsive switching of D–π–A naphthalimide alignments along the nanotube between a left-handed chiral and random arrangement was observed. The peptide nanotube is a stable scaffold for attaining pH-responsive alignment switching of side-chain chromophores.

Double-click synthesis of polysiloxane third-order nonlinear optical polymers with donor–acceptor chromophores

A series of third-order nonlinear polysiloxane polymer materials were prepared by thiol–ene click polymerization and [2 + 2] click chemistry. All the polymers exhibit good electron transfer capabilities and nonlinear optical properties.

Near‐Infrared Optogenetic Genome Engineering Based on Photon‐Upconversion Hydrogels

AbstractPhoton upconversion (UC) from near‐infrared (NIR) light to visible light has enabled optogenetic manipulations in deep tissues. However, materials for NIR optogenetics have been limited to inorganic UC nanoparticles. Herein, NIR‐light‐triggered optogenetics using biocompatible, organic TTA‐UC hydrogels is reported. To achieve triplet sensitization even in highly viscous hydrogel matrices, a NIR‐absorbing complex is covalently linked with energy‐pooling acceptor chromophores, which significantly elongates the donor triplet lifetime. The donor and acceptor are solubilized in hydrogels formed from biocompatible Pluronic F127 micelles, and heat treatment endows the excited triplets in the hydrogel with remarkable oxygen tolerance. Combined with photoactivatable Cre recombinase technology, NIR‐light stimulation successfully performs genome engineering resulting in the formation of dendritic‐spine‐like structures of hippocampal neurons.

Near-Infrared Optogenetic Genome Engineering Based on Photon-Upconversion Hydrogels.

Photon upconversion (UC) from near-infrared (NIR) light to visible light has enabled optogenetic manipulations in deep tissues. However, materials for NIR optogenetics have been limited to inorganic UC nanoparticles. Herein, NIR-light-triggered optogenetics using biocompatible, organic TTA-UC hydrogels is reported. To achieve triplet sensitization even in highly viscous hydrogel matrices, a NIR-absorbing complex is covalently linked with energy-pooling acceptor chromophores, which significantly elongates the donor triplet lifetime. The donor and acceptor are solubilized in hydrogels formed from biocompatible Pluronic F127 micelles, and heat treatment endows the excited triplets in the hydrogel with remarkable oxygen tolerance. Combined with photoactivatable Cre recombinase technology, NIR-light stimulation successfully performs genome engineering resulting in the formation of dendritic-spine-like structures of hippocampal neurons.

Giant Proteinosomes As Scaffolds for Light Harvesting.

Based on an interfacial assembly strategy, a giant proteinosome was successfully fabricated by using protein-surfactant as building blocks, which formed a thin protein layer as a membrane. This approach of making protein assemblies was very facile, and it was very convenient to remove the templates of oil and get water-filled proteinosomes by dialysis. Through modifying acceptor and donor chromophores on the protein monomers, an efficient artificial light-harvesting system was successfully fabricated on the proteinosome, which was a scaffold for efficient light harvesting. Furthermore, the on-off switchable energy transfer was realized by protein folding and unfolding. The efficient artificial light-harvesting systems we designed as the potential platforms could be utilized for biomaterials.

Photoswitchable J-Aggregated Processable Organogel by Integrating a Photochromic Acceptor.

A novel π-chromophoric 1,4-bis(anthracenylethynyl)benzene (BAB)-based highly emissive J-aggregated organogel has been synthesized and characterized. Single-crystal structure determination of asymmetric π-chromophoric bola-amphiphilic BAB1 (dodecyl and triethyleneglycolmonomethylether containing side chains of bis(anthracenylethynyl)benzene) supports J-aggregation. Further, a photochromic acceptor chromophore, 4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-2-carbaldehyde), is noncovalently encapsulated in the gel and photoswitching studies have been performed based on photochromic Förster resonance energy transfer. The modulated emission of the processable soft material is further exploited for rewritable display. However, BAB2 (dodecyl side chain on both sides) does not show gelation property due to its low solubility.

Homo-FRET in π-Conjugated Polygons: Intermediate-Strength Dipole-Dipole Coupling Makes Energy Transfer Reversible.

The concept of homo-FRET is often used to describe energy transfer between like chromophores of molecular aggregates such as in π-conjugated polymers. Homo-FRET is revealed by a dynamic depolarization in fluorescence but strictly only applies to the limit of weak dipole-dipole coupling, where energy transfer occurs on time scales much longer than those of nuclear relaxation. By considering the polarization anisotropy of photoluminescence emission and excitation of model multichromophoric aggregates on the single-molecule level, we demonstrate the transition of energy-transfer dynamics from the case of weak coupling to that of strong coupling, revealing the elusive regime of intermediate-strength coupling where energy transfer between degenerate donor and acceptor chromophores becomes reversible so that information on the excitation route of the emitting chromophore is lost.

Unraveling Excitonic Effects for the First Hyperpolarizabilities of Chromophore Aggregates

Excitonic interactions often significantly affect the optoelectronic properties of molecular materials. However, their role in determining the nonlinear optical response of organic electro-optic materials remains poorly understood. In this paper, we explore the effects of excitonic interactions on the first hyperpolarizability for aggregates of donor–acceptor chromophores. We show that calculations of the first hyperpolarizabilty of chromophore aggregates based on a two-state model agree well with the more rigorous coupled perturbed Hartree–Fock method. We then use both time-dependent density functional theory calculations and the molecular exciton approximation to parametrize the two-state model. Use of the molecular exciton approximation to the two-state model (i) is appropriate for disordered aggregates (unlike band theory), (ii) is computationally efficient enough for calculating the first hyperpolarizability of materials that consist of thousands of interacting chromophores, and (iii) allows the unra...

Constructing Artificial Light-Harvesting Systems by Covalent Alignment of Aggregation-Induced Emission Molecules.

The characteristics of chloroplasts harvesting solar energy and conducting energy transfer have inspired chemists to mimic similar processes. However, accurate manipulation to gain regularly displayed antenna chromophores in mimicking chloroplasts is a great challenge. Herein, a rational design is presented that combines orderly arranged chromophores with aggregation-induced emission (AIE) to develop artificial light-harvesting systems. Tetraphenyl ethylene (TPE) molecules, which exhibited strong AIE properties, are considered as building blocks to fabricate high emissive 2D nanosheets and nanovesicles, respectively. Furthermore, the well-aligned TPE molecules are also developed as donor chromophores in light-harvesting processes. After subsequent surface modification by porphyrin molecules as acceptor chromophores, an efficient light-harvesting system has been integrally constructed. This study demonstrates a novel strategy to utilize AIE feature to mimic chloroplasts process in nature.