Directing charge transfer in perylene based light-harvesting antenna molecules.

Directing energy and charge transfer processes in light-harvesting antenna systems is quintessential for optimizing the efficiency of molecular devices for artificial photosynthesis. In this work, we report a novel synthetic method to construct two regioisomeric antenna molecules (1-D2A2 and 7-D2A2), in which the 4-(n-butylamino)naphthalene monoimide energy and electron donor is attached to the perylene monoimide diester (PMIDE) acceptor at the 1- and 7-bay positions, respectively. The non-symmetric structure of PMIDE renders a polarized distribution of the frontier molecular orbitals along the long axis of this acceptor moiety, which differentiates the electron coupling between the donor, attached at either the 1- or the 7-position, and the acceptor. We demonstrate that directional control of the photo-driven charge transfer process has been obtained by engineering the molecular structure of the light-harvesting antenna molecules.

Perylene Bisimide Dyes with up to Five Independently Introduced Substituents: Controlling the Functionalization Pattern and Photophysical Properties Using Regiospecific Bay Substitution.

We report herein a versatile and user-friendly synthetic methodology based on sequential functionalization that enables the synthesis of previously unknown perylene bisimide (PBI) dyes with up to five different substituents attached to the perylene core (e.g., compound 15). The key to the success of our strategy is a highly efficient regiospecific 7-mono- and 7,12-di-phenoxy bay substitution at the "imide-activated" 7- and 12-bay positions of 1,6,7,12-tetrachloroperylene monoimide diester 1. The facile subsequent conversion of the diester groups into an imide group resulted in novel PBIs (e.g., compound 14) with two phenoxy substituents specifically at the 7- and 12-bay positions. This conversion led to the activation of C-1 and C-6 bay positions, and thereafter, the remaining two chlorine atoms were substituted to obtain tetraphenoxy-PBI (compound 15) that has two different imide and three different bay substituents. The methodology provides excellent control over the functionalization pattern, which enables the synthesis of various regioisomeric pairs bearing the same bay substituents. Another important feature of this strategy is the high sensitivity of HOMO-LUMO energies and photoinduced charge transfer toward sequential functionalization. As a result, systematic fluorescence on-off switching has been demonstrated upon subsequent substitution with the electron-donating 4-methoxyphenoxy substituent.

A Molecular Level Approach To Elucidate the Supramolecular Packing of Light-Harvesting Antenna Systems.

The molecular geometry and supramolecular packing of two bichromophoric prototypic light harvesting compounds D1A2 and D2A2, consisting of two naphthylimide energy donors that were attached to the 1,7 bay positions of a perylene monoimide diester energy acceptor, have been determined by a hybrid approach using magic angle spinning NMR spectroscopy and electron nano-crystallography (ENC), followed by modelling. NMR shift constraints, combined with the P 1 ‾ space group obtained from ENC, were used to generate a centrosymmetric dimer of truncated perylene fragments. This racemic packing motif is used in a biased molecular replacement approach to generate a partial 3D electrostatic scattering potential map. Resolving the structure of the bay substituents is guided by the inversion symmetry, and the distance constraints obtained from heteronuclear correlation spectra. The antenna molecules form a pseudocrystalline lattice of antiparallel centrosymmetric dimers with pockets of partially disordered bay substituents. The two molecules in a unit cell form a butterfly-type arrangement. The hybrid methodology that has been developed is robust and widely applicable for critical structural underpinning of self-assembling structures of large organic molecules.

Substitution Effects on the Photoinduced Charge-Transfer Properties of Novel Perylene-3,4,9,10-tetracarboxylic Acid Derivatives.

We report here the synthesis and photophysical study of a series of electron donor-acceptor molecules, in which electron-donating 4-methoxyphenoxy groups are attached to the 1,7-bay positions of four different perylene tetracarboxylic acid derivatives, namely, perylene tetraesters 1, perylene monoimide diesters 2, perylene bisimides 3, and perylene monobenzimidazole monoimides 4. These perylene derivatives are used because of their increasing order of electron-accepting capability upon moving from 1 to 4. Two additional donor-acceptor molecules are synthesized by linking electron-donating 4-methoxyphenyl groups to the imide position of perylene monoimide diester 2 and perylene bisimide 3. The motivation for this study is to achieve a good control over the photoinduced charge-transfer (CT) process in perylene-based systems by altering the position of electron donors and tuning the electron deficiency of perylene core. A comprehensive study of the photophysical properties of these molecules has shown a highly systematic trend in the magnitude of CT as a function of increased electron deficiency of the perylene core and solvent polarity. Importantly, just by changing the attachment of electron-donating group from "bay" to "imide" position, we are able to block the CT process. This implies that the positioning of the electron donor at the perylene core strongly influences the kinetics of the photoinduced CT process. In these compounds, the CT process is characterized by the quenching of fluorescence and singlet excited-state lifetimes as compared to model compounds bearing non-electron-donating 4-tert-butylphenoxy groups. Transient absorption spectroscopy did not reveal spectra of CT states. This most likely implies that the CT state is not accumulated, because of the faster charge recombination.

Fluorescent PET probes based on perylene-3,4,9,10-tetracarboxylic tetraesters.

Perylene-3,4,9,10-tetracarboxylic tetraester-based fluorescent PET probes with aniline receptors attached either at the peri- or the bay-positions have been synthesized. By attaching aniline receptors at the bay position, pH-sensitive "light-up" probes, with fluorescence quantum yields ΦF > 0.75 and fluorescent enhancements FE > 500 in ethanol, have been obtained.

Protein detection on biotin-derivatized polyallylamine by optical microring resonators.

Silicon optical microring resonators (MRRs) are sensitive devices that can be used for biosensing. We present a novel biosensing platform based on the application of polyelectrolyte (PE) layers on such MRRs. The top PE layer was covalently labeled with biotin to ensure binding sites for antibodies via a streptavidin-biotin binding scheme. Monitoring the shift in the microring resonance wavelength allows real-time, highly sensitive detection of the biomolecular interaction.

Synthesis of regioisomerically pure 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid derivatives.

The perylene derivative 1,7-dibromoperylene-3,4,9,10-tetracarboxylic tetrabutylester has been obtained in regioisomerically pure form, by employing a highly efficient, scalable, and robust synthesis starting from commercially available perylene-3,4,9,10-tetracarboxylic bisanhydride. Subsequently, this compound is utilized for the synthesis of extremely valuable and versatile regioisomerically pure intermediates, namely, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dibutylester monoanhydride, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic bisanhydride, and 1,7-dibromoperylene monoimid monoanhydride. These compounds possess at least one anhydride functionality in addition to the 1,7 bromo substituents and thus allow for a virtually limitless attachment of substituents both at the "peri" and the "bay" positions. The intermediate 1,7-dibromoperylene monoimide monoanhydride is of special interest as it provides access to unsymmetrically imide-substituted 1,7-dibromoperylene derivatives, which are not accessible by previously known procedures. Finally, substitution of the 1,7 bromine atoms in the bay area by phenoxy groups, which is a generally applied reaction for 1,7-dibromoperylene bisimides, was proven to be equally effective for a 1,7-dibromoperylene tetraester and a 1,7-dibromoperylene diester monoimid.

Controlled amino-functionalization by electrochemical reduction of bromo and nitro azobenzene layers bound to Si(111) surfaces.

4-Nitrobenzenediazonium (4-NBD) and 4-bromobenzenediazonium (4-BBD) salts were grafted electrochemically onto H-terminated, p-doped silicon (Si) surfaces. Atomic force microscopy (AFM) and ellipsometry experiments clearly showed layer thicknesses of 2-7 nm, which indicate multilayer formation. Decreasing the diazonium salt concentration and the reaction time resulted in a smaller layer thickness, but did not prevent the formation of multilayers. It was demonstrated, mainly by X-ray photoelectron spectroscopy (XPS), that the diazonium salts not only react with the H-terminated Si surface, but also with electrografted phenyl groups via azo-bond formation. These azo bonds can be electrochemically reduced at Ered = -1.5 V, leading to the corresponding amino groups. This reduction resulted in a modest decrease in layer thickness, and did not yield monolayers. This indicates that other coupling reactions, notably a biphenyl coupling, induced by electrochemically produced phenyl radicals, take place as well. In addition to the azo functionalities, the nitro functionalities in electrografted layers of 4-NBD were independently reduced to amino functionalities at a lower potential (Ered = -2.1 V). The presence of amino functionalities on fully reduced layers, both from 4-NBD- and 4-BBD-modified Si, was shown by the presence of fluorine after reaction with trifluoroacetic anhydride (TFAA). This study shows that the electrochemical reduction of azo bonds generates amino functionalities on layers produced by electrografting of aryldiazonium derivatives. In this way multifunctional layers can be formed by employing functional aryldiazonium salts, which is believed to be very practical in the fabrication of sensor platforms, including those made of multi-array silicon nanowires.

Direct Imaging of Local pH Reveals Bubble-Induced Mixing in a CO2 Electrolyzer.

Electrochemical CO2 reduction poses a promising pathway to produce hydrocarbon chemicals and fuels without relying on fossil fuels. Gas diffusion electrodes allow high selectivity for desired carbon products at high current density by ensuring a sufficient CO2 mass transfer rate to the catalyst layer. In addition to CO2 mass transfer, the product selectivity also strongly depends on the local pH at the catalyst surface. In this work, we directly visualize for the first time the two-dimensional (2D) pH profile in the catholyte channel of a gas-fed CO2 electrolyzer equipped with a bipolar membrane. The pH profile is imaged with operando fluorescence lifetime imaging microscopy (FLIM) using a pH-sensitive quinolinium-based dye. We demonstrate that bubble-induced mixing plays an important role in the Faradaic efficiency. Our concentration measurements show that the pH at the catalyst remains lower at -100 mA cm-2 than at -10 mA cm-2, implying that bubble-induced advection outweighs the additional OH- flux at these current densities. We also prove that the pH buffering effect of CO2 from the gas feed and dissolved CO2 in the catholyte prevents the gas diffusion electrode from becoming strongly alkaline. Our findings suggest that gas-fed CO2 electrolyzers with a bipolar membrane and a flowing catholyte are promising designs for scale-up and high-current-density operation because they are able to avoid extreme pH values in the catalyst layer.

Quinolinium-Based Fluorescent Probes for Dynamic pH Monitoring in Aqueous Media at High pH Using Fluorescence Lifetime Imaging.

Spatiotemporal pH imaging using fluorescence lifetime imaging microscopy (FLIM) is an excellent technique for investigating dynamic (electro)chemical processes. However, probes that are responsive at high pH values are not available. Here, we describe the development and application of dedicated pH probes based on the 1-methyl-7-amino-quinolinium fluorophore. The high fluorescence lifetime and quantum yield, the high (photo)stability, and the inherent water solubility make the quinolinium fluorophore well suited for the development of FLIM probes. Due to the flexible fluorophore-spacer-receptor architecture, probe lifetimes are tunable in the pH range between 5.5 and 11. An additional fluorescence lifetime response, at tunable pH values between 11 and 13, is achieved by deprotonation of the aromatic amine at the quinolinium core. Probe lifetimes are hardly affected by temperature and the presence of most inorganic ions, thus making FLIM imaging highly reliable and convenient. At 0.1 mM probe concentrations, imaging at rates of 3 images per second, at a resolution of 4 µm, while measuring pH values up to 12 is achieved. This enables the pH imaging of dynamic electrochemical processes involving chemical reactions and mass transport.

Tuning the Driving Force for Charge Transfer in Perovskite-Chromophore Systems.

Understanding the interplay between the kinetics and energetics of photophysical processes in perovskite-chromophore hybrid systems is crucial for realizing their potential in optoelectronics, photocatalysis, and light-harvesting applications. By combining steady-state optical characterizations and transient absorption spectroscopy, we have investigated the mechanism of interfacial charge transfer (CT) between colloidal CsPbBr3 nanoplatelets (NPLs) and surface-anchored perylene derivatives and have explored the possibility of controlling the CT rate by tuning the driving force. The CT driving force was tuned systematically by attaching acceptors with different electron affinities and by varying the bandgap of NPLs via thickness-controlled quantum confinement. Our data show that the charge-separated state is formed by selectively exciting either the electron donors or acceptors in the same system. Upon exciting attached acceptors, hole transfer from perylene derivatives to CsPbBr3 NPLs takes place on a picosecond time scale, showing an energetic behavior in line with the Marcus normal regime. Interestingly, such energetic behavior is absent upon exciting the electron donor, suggesting that the dominant CT mechanism is energy transfer followed by ultrafast hole transfer. Our findings not only elucidate the photophysics of perovskite-molecule systems but also provide guidelines for tailoring such hybrid systems for specific applications.

Micellization behavior of aromatic moiety bearing hybrid fluorocarbon sulfonate surfactants.

Aggregation behavior and thermodynamic properties of two novel homologous aromatic moiety bearing hybrid fluorocarbon surfactants, sodium 2-(2-(4-ethylphenyl)-1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate (1) and sodium 2-(1,1,2,2-tetrafluoro-2-(4-vinylphenyl)ethoxy)-1,1,2,2-tetrafluoroethanesulfonate (2) were studied using surface tension measurements and isothermal titration calorimetry (ITC) in dilute aqueous solutions at room temperature. Because of the aromatic group in the hydrophobic tail, both surfactants are soluble at room temperature unlike their starting precursor, 5-iodooctafluoro-3-oxapentanesulfonate as well as several other fluorocarbon sulfonic acid salts. Moreover, the surfactant 2 has the ability that it can be polymerized once microemulsions are formed with it. The ionic conductivity measurements of 1 at five different temperatures from 288 to 313 K were carried out to study the effect of temperature on the micellization and its thermodynamics. The pseudophase separation model was applied to estimate thermodynamic quantities from conductivity data. The Gibbs energy of micellization versus temperature exhibited the characteristic U-shaped behavior with a minimum at 306 K. The micellization process was found to be largely entropy driven. Because of its hybrid structure, the entropy change of micellization for 1 was larger than what is common for hydrocarbon surfactants like SDS but less than for fully fluorinated surfactants like NaPFO. The micellization process was found to be following the entropy-enthalpy compensation phenomena.

Fast Charge Separation in Distant Donor-Acceptor Dyads Driven by Relaxation of a Hot Excited State.

A series of three perylenemonoimide-p-oligophenylene-dimethylaniline molecular dyads undergo photoinduced charge separation (CS) with anomalous distance dependence as a function of increasing donor-acceptor (DA) distances. A comprehensive experimental and computational investigation of the photodynamics in the donor-bridge-acceptor (DBA) chromophores reveals a clear demarcation concerning the nature of the CS accessed at shorter (bridgeless) and longer DA distances. At the shortest distance, a strong DA interaction and ground-state charge delocalization populate a hot excited state (ES) with prominent charge transfer (CT) character, via Franck-Condon vertical excitation. The presence of such a CT-polarized hot ES enables a subpicosecond CS in the bridgeless dyad. The incorporation of the p-oligophenylene bridge effectively decouples the donor and the acceptor units in the ground state and consequentially suppresses the CT polarization in the hot ES. Theoretically, this should render a slower CS at longer distances. However, the transient absorption measurement reveals a fast CS process at the longer distance, contrary to the anticipated exponential distance dependence of the CS rates. A closer look into the excited-state dynamics suggests that the hot ES undergoes ultrafast geometry relaxation (τ < 1 ps) to create a relaxed ES. As compared to a decoupled, twisted geometry in the hot ES, the geometry of the relaxed ES exhibits a more planar conformation of the p-oligophenylene bridges. Planarization of the bridge endorses an increased charge delocalization and a prominent CT character in the relaxed ES and forms the origin for the evident fast CS at the longest distance. Thus, the relaxation of the hot ES and the concomitantly enhanced charge delocalization adds a new caveat to the classic nature of distance-dependent CS in artificial DBA chromophores and recommends a cautious treatment of the attenuation factor (ß) while discussing anomalous CS trends.

Room temperature synthesis of perylene diimides facilitated by high amic acid solubility.

A novel protocol for the synthesis of perylene diimides (PDIs), by reacting perylene dianhydride (PDA) with aliphatic amines is reported. Full conversions were obtained at temperatures between 20 and 60 °C, using DBU as the base in DMF or DMSO. A "green" synthesis of PDIs, that runs at higher temperatures, was developed using K2CO3 in DMSO. The reaction sequence for the imidization process, via perylene amic acid intermediates (PAAs), has been confirmed experimentally aided by the synthesis and full characterization of stable model amic acid salts and amic esters. Kinetic studies, using absorption spectroscopy, have established that PDI formation proceeds via fast amic acid formation, followed by a slow conversion to imides. Solubility of the intermediate PAA salts is found to be low and rate-limiting. Based on this finding, quantitative PDI synthesis at room temperature was achieved by diluting the reaction mixture with water, the solvent in which PAA salts have better solubility. Thus, the otherwise harsh synthesis of PDIs has been transformed into an extremely convenient functional group tolerant and highly efficient reaction that runs at room temperature.

Synthesis of a polymerizable fluorosurfactant for the construction of stable nanostructured proton-conducting membranes.

The synthesis of the polymerizable fluorinated surfactant sodium 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-(4-vinylphenyl)ethoxy)ethanesulfonate (1) and a number of related fluorocarbon compounds is described. Compound 1 is synthesized using a copper-mediated cross-coupling reaction of 4-bromobenzaldehyde and sodium 5-iodooctafluoro-3-oxapentanesulfonate. The resulting benzaldehyde is converted to a styrene unit using a Wittig reaction with methyltriphenylphosphonium bromide in acetonitrile, using DBU as a base. This strategy for converting an iodo-functionalized fluorosurfactant to a styrene-containing fluorosurfactant is highly efficient because both reactions are performed in polar solvents and are compatible with the sulfonate moiety. In addition, the copper-mediated cross-coupling reaction is most efficient with electron-poor aryl bromides like 4-bromobenzaldehyde. We wish to employ 1 for the construction of nanostructured membranes by polymerization of 1 in a microemulsion or in lyotropic liquid crystalline phases.

Highly sensitive water-soluble fluorescent ph sensors based on the 7-amino-1-methylquinolinium chromophore.

Highly sensitive water-soluble fluorescent pH sensors have been synthesized employing the 7-amino-1-methylquinolinium (7AMQ) chromophore. These compounds, which contained oligomethylene spacers and substituted amine receptor units, were prepared in high yields and purity by a single reaction from the readily available 7-fluoro-1-methylquinolinium iodide. Density functional theory (DFT) and semiempirical INDO/s calculations have been performed to describe the ground state and the locally excited state of the chromophore. The photophysics and the sensor characteristics have been investigated. Dissociation constants pK(A)* ranging from 5.8 to 9.9 have been obtained. An additional quenching process at pH 11, due to excited state deprotonation at N7, has been observed. Fluorescence quantum yields in the protonated "on-state" between 0.75 and 0.85 and fluorescence enhancements (FE) between 2 and 55 were determined. These values are significantly higher than those of molecules based on other CT-chromophores that contain identical spacer-receptor units. The high fluorescence enhancements may be explained by the low rate of fluorescence ( approximately 6 x 10(7) s(-1)) and the high excited state reduction potential ( approximately 1.6 eV) of the 7AMQ chromophore.

Efficacious elimination of intramolecular charge transfer in perylene imide based light-harvesting antenna molecules.

Two light-harvesting antenna molecules were obtained by positioning naphthalene monoimide energy donors at the imide position, instead of the bay positions, of perylene imide energy acceptors. Such rational design resulted in a complete suppression of parasitic intramolecular charge transfer without compromising the desired ultrafast rates of excitation energy transfer.

Overcoming the exciton binding energy in two-dimensional perovskite nanoplatelets by attachment of conjugated organic chromophores.

In this work we demonstrate a novel approach to achieve efficient charge separation in dimensionally and dielectrically confined two-dimensional perovskite materials. Two-dimensional perovskites generally exhibit large exciton binding energies that limit their application in optoelectronic devices that require charge separation such as solar cells, photo-detectors and in photo-catalysis. Here, we show that by incorporating a strongly electron accepting moiety, perylene diimide organic chromophores, on the surface of the two-dimensional perovskite nanoplatelets it is possible to achieve efficient formation of mobile free charge carriers. These free charge carriers are generated with ten times higher yield and lifetimes of tens of microseconds, which is two orders of magnitude longer than without the peryline diimide acceptor. This opens a novel synergistic approach, where the inorganic perovskite layers are combined with functional organic chromophores in the same material to tune the properties for specific applications.

Scalable Route to Electroactive and Light Active Perylene Diimide Dye Polymer Binder for Lithium-Ion Batteries.

Developing multifunctional polymeric binders is key to the design of energy storage technologies with value-added features. We report that a multigram-scale synthesis of perylene diimide polymer (PPDI), from a single batch via polymer analogous reaction route, yields high molecular weight polymers with suitable thermal stability and minimized solubility in electrolytes, potentially leading to improved binding affinity toward electrode particles. Further, it develops strategies for designing copolymers with virtually any desired composition via a subsequent grafting, leading to purpose-built binders. PPDI dye as both binder and electroactive additive in lithium half-cells using lithium iron phosphate exhibits good electrochemical performance.

Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity.

The excited-state dynamics of perylene-based bichromophoric light harvesting antenna systems has been tailored by systematic modification of the molecular structure and by using solvents of increasing polarity in the series toluene, chloroform, and benzonitrile. The antenna systems consist of blue light absorbing naphthalene monoimide (NMI) energy donors (D1, D2, and D3) and the perylene derived green light absorbing energy acceptor moieties, 1,7-perylene-3,4,9,10-tetracarboxylic tetrabutylester (A1), 1,7-perylene-3,4,9,10-tetracarboxylic monoimide dibutylester (A2), and 1,7-perylene-3,4,9,10-tetracarboxylic bisimide (A3). The design of these antenna systems is such that all exhibit ultrafast excitation energy transfer (EET) from the excited donor to the acceptor, due to the effective matching of optical properties of the constituent chromophores. At the same time, electron transfer from the donor to the excited acceptor unit has been limited by the use of a rigid and nonconjugated phenoxy bridge to link the donor and acceptor components. The antenna molecules D1A1, D1A2, and D1A3, which bear the least electron-rich energy donor, isopentylthio-substituted NMI D1, exhibited ultrafast EET (τEET ∼ 1 ps) but no charge transfer and, resultantly, emitted a strong yellow-orange acceptor fluorescence upon excitation of the donor. The other antenna molecules D2A2, D2A3, and D3A3, which bear electron-rich energy donors, the amino-substituted NMIs D2 and D3, exhibited ultrafast energy transfer that was followed by a slower (ca. 20-2000 ps) electron transfer from the donor to the excited acceptor. This charge transfer quenched the acceptor fluorescence to an extent determined by molecular structure and solvent polarity. These antenna systems mimic the primary events occurring in the natural photosynthesis, i.e., energy capture, efficient energy funneling toward the central chromophore, and finally charge separation, and are suitable building blocks for achieving artificial photosynthesis, because of their robustness and favorable and tunable photophysical properties.