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 CO...

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...

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...

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....

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)...

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...

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...

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...

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...

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)...

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...

Novel derivatives of 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid: Synthesis, electrochemical and optical properties

A family of novel unsymmetrical "peri"-substituted perylene-3,4,9,10-tetracarboxylic acid derivatives (5-10), with 1,6,7,12-tetrachloro-substituents at the bay-positions, has been synthesized. Subsequently, their redox and optical properties have been explored with the intent of unveiling opto-electronic characteristics of these newly...

Tunable and highly efficient light-harvesting antenna systems based on 1,7-perylene-3,4,9,10-tetracarboxylic acid derivatives

We report the synthesis and excited-state dynamics of a series of five bichromophoric light-harvesting antenna systems, which are capable of efficient harvesting of solar energy in the spectral range of 350–580 nm. These antenna systems have been synthesized in a modular fashion by the covalent attachment of blue light absorbing naphthalene...

Tunable and highly efficient light-harvesting antenna systems based on 1,7-perylene-3,4,9,10-tetracarboxylic acid derivatives

We report the synthesis and excited-state dynamics of a series of five bichromophoric light-harvesting antenna systems, which are capable of efficient harvesting of solar energy in the spectral range of 350–580 nm. These antenna systems have been synthesized in a modular fashion by the covalent attachment of blue light absorbing naphthalene...

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...

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....

High charge carrier mobility and efficient charge separation in highly soluble perylenetetracarboxyl-diimides

In this communication we report on the synthesis and charge mobility of highly soluble perylenebisimid derivatives.We show that introduction of alkylester side chains results in compounds combining a high solubility with charge mobilities up to 0.22 cm2 V_1 s_1. These materials are therefore interesting as an electron acceptor for solution...