Publications by Lukas Pfeifer | EPFL Graph Search

Architecture-Controllable Single-Crystal Helical Self-assembly of Small-Molecule Disulfides with Dynamic Chirality

Beyond the common supramolecular helical polymers in solutions, controlling single-crystal helical self-assembly with precisely defined chirality and architectures has been challenging. Here, we report that simply merging static homochiral amino acids with dynamic chiral disulfides can produce a class of building blocks featuring supramolecular helical single-crystal self-assembly with unusual stereodivergency. Analysis of 20 single-crystal structures of 1,2-dithiolanes gives an atom-precision understanding of the chirality transfer from the molecular to supramolecular level, featuring homochiral and heterochiral helical supramolecular self-assembly in the solid state. The underlying structure-assembly relationship reveals that the synergistic interplay of intermolecular H-bonds and the 1,2-dithiolane ring with adaptive chirality plays a key role in determining the assembly pathway, also involving the effects of residue groups, substituents, molecular stacking, and solvents. The confinement effect in the solid state can stabilize the dynamic stereochemistry of disulfide bonds and selectively result in specific conformers that can minimize the energy of global supramolecular systems. We envision that these results represent a starting point to use dynamic chiral disulfide as a functional entity in supramolecular chemistry and may inspire a new class of supramolecular helical polymers with dynamic functions.

AMER CHEMICAL SOC2023

Coupled Rotary and Oscillatory Motion in a Second-Generation Molecular Motor Pd Complex

Lukas Pfeifer

Molecular machines offer many opportunities for the development of responsive materials and introduce autono-mous motion in molecular systems. While basic molecular switches and motors carry out one type of motion upon being exposed to an external stimulus, the development of molecular systems capable of performing coupled motions is essential for the development of more advanced molecular machinery. Overcrowded alkene-based rotary molecular motors are an ideal basis for the design of such systems as they undergo a controlled rotation initiated by light allowing for excellent spatio-temporal precision. Here, we present an example of a Pd complex of a second-generation rotary motor whose Pd center undergoes a coupled oscillatory motion relative to the motor core upon rotation of the motor. We have studied this phenomenon by UV-vis, NMR, and density functional theory calculations to support our conclusions. With this demonstration of a coupled rotation-oscillation motion powered by a light-driven molecular motor, we provide a solid basis for the development of more advanced molecular machines integrating different types of motion in their operation.

AMER CHEMICAL SOC2023

Dataset of "The Impact of Spacer Size on Charge Transfer Excitons in Dion-Jacobson and Ruddlesden-Popper Layered Hybrid Perovskites"

Masaud Hassan S Almalki, George Cameron Fish, Michael Graetzel, Jacques-Edouard Moser, Lukas Pfeifer, Aaron Tomas Terpstra

This dataset underpins the following article published in the Journal of Physical Chemistry Letters: "The Impact of Spacer Size on Charge Transfer Excitons in Dion-Jacobson and Ruddlesden-Popper Layered Hybrid Perovskites" DOI: 10.1021/acs.jpclett.3c01125 The dataset contains steady state absorption (UV/Vis), transient absorption (TA) and electroabsorption (EA) data acquired from experiments on 2D perovskites incorporating different organic spacers. The dataset also includes data acquired from temperature dependent measurements. The transient absorption data has been treated using a home-written matlab script in order to correct for the chirp.

EPFL Infoscience2023

Optoelectronic or photovoltaic device with metal halide perovskite film treated by passivating agent

Michael Graetzel, Anurag Krishna, Lukas Pfeifer, Shaik Mohammed Zakeeruddin

This invention relates to an optoelectronic or photovoltaic device comprising a perovskite or metal halide perovskite film treated by one or more compounds of formula (I): ((R1-NH(R2)-R3)+)nW (I), wherein n is an integer selected from 1, 2, or 3; R1, R2, R3 are independently selected from a hydrocarbyl group containing 1-40 carbon atoms said hydrocarbyl group, if said hydrocarbyl group comprises 3 or more carbons, may be linear or branched; and W is an anion.

2023

Surface Passivation of FAPbI3-Rich Perovskite with Cesium Iodide Outperforms Bulk Incorporation

Essa Awadh R Alharbi, Thomas Paul Baumeler, Brian Irving Carlsen, Felix Thomas Eickemeyer, George Cameron Fish, Jing Gao, Michael Graetzel, Mounir Driss Mensi, Jacques-Edouard Moser, Lukas Pfeifer, Kevin Sivula, Jun Ho Yum, Shaik Mohammed Zakeeruddin

Metal halide perovskites (MHPs) have shown an incredible increase in efficiency, reaching as high as 25.7%, which now competes with traditional photovoltaic technologies. Herein, we excluded CsX and RbX (X = I–, Br–, Cl–), the most commonly used cations to stabilize α-FAPbI3, from the bulk of perovskite thin films and applied them on the surface as passivation agents. Extensive device optimization led to a power conversion efficiency (PCE) of 24.1% with a high fill factor (FF) of 82.2% upon passivation with CsI. We investigated in depth the effect of CsI passivation on structural and optoelectronic properties using X-ray diffraction (XRD), angle-resolved X-ray photoelectron spectroscopy (ARXPS), Kelvin probe force microscopy (KPFM), time-resolved photoluminescence (TRPL), photoluminescence quantum yield (PLQY), and electroabsorption spectroscopy (TREAS). Furthermore, passivated devices exhibit enhanced operational stability, with optimized passivation with CsI leading to a retention of ∼90% of the initial PCE under 1 sun illumination with maximum power point tracking for 600 h.

2023

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Organic materials can tune the optical properties in layered (2D) hybrid perovskites, although their impact on photophysics is often overlooked. Here, we use transient absorption spectroscopy to probe the Dion−Jacobson (DJ) and Ruddlesden−Popper (RP) 2D perovskite phases. We show the formation of charge transfer excitons in DJ phases, resulting in a photoinduced Stark effect which is shown to be dependent on the spacer size. By using electroabsorption spectroscopy, we quantify the strength of the photoinduced electric field, while temperature-dependent measurements demonstrate new features in the transient spectra of RP phases at low temperatures resulting from the quantum-confined Stark effect. This study reveals the impact of spacer size and perovskite phase configuration on charge transfer excitons in 2D perovskites of interest to their advanced material design.

2023

Molecular machines have caused one of the greatest paradigm shifts in chemistry, and by powering artificial mechanical molecular systems and enabling autonomous motion, they are expected to be at the heart of exciting new technologies. One of the biggest challenges that still needs to be addressed is designing the involved molecules to combine different orthogonally controllable functions. Here, we present a prototype of artificial molecular motors exhibiting the dual function of rotary motion and photoluminescence. Both properties are controlled by light of different wavelengths or by exploiting motors' outstanding two-photon absorption properties using low-intensity near-infrared light. This provides a noninvasive way to both locate and operate these motors in situ, essential for the application of molecular machines in complex (bio)environments.

AMER ASSOC ADVANCEMENT SCIENCE2022

Mechanistic Insight into Supramolecular Polymerization in Water Tunable by Molecular Geometry

Lukas Pfeifer, Fan Xu

Supramolecular self-assembly in water based on non-covalent bonding is attracting major attention due to the potential of hydrogels and aqueous polymers in biomedical applications. Although supramolecular polymerization in organic solvents is well established, the key design features, the assembly mechanisms in water and achieving control over the aggregate structures remain challenging. Here, we present the assembly and disassembly of geometrical isomers of a stiff-stilbene bis-urea amphiphile (SA) in pure water. A remarkable feature of this system is that the (E)-isomer forms supramolecular polymers in both pure water and organic solvents. Taking advantage of this unique property, the hydrophobic effect was studied by comparing the supramolecular assembly in both systems. The assembly process in water follows an enthalpy-driven nucleation-elongation (cooperative) supramolecular polymerization mechanism with a standard Gibbs free energy (Delta G degrees = -53 kJ mol(-1)) double the value of the one found in toluene. We attributed this distinctive feature to the hydrophobic effect in water. Furthermore, we discovered an isomer-dependent assembly process, which can be used to control aggregation in aqueous media. Due to the substantial geometric difference between (E)-SA and (Z)-SA, we compared their assembly in water to study the influence of different driving forces involved in the process. The supramolecular polymerization of (E)-SA was cooperatively influenced by hydrogen bonding, pi-stacking, and hydrophobic effects, whereas the assembly of (Z)-SA was mainly driven by hydrophobic effects. As a result, the fiber length of (E)-SA in water is much longer than that of (Z)-SA, presenting opportunities for geometrical control of aggregation in aqueous media. [GRAPHICS]

CHINESE CHEMICAL SOC2022

Visible light activated BINOL-derived chiroptical switches based on boron integrated hydrazone complexes

Lukas Pfeifer

Chiral optical switches, which use light to control chirality in a reversible manner, offer unique properties and fascinating prospects in the areas of molecular switching and responsive systems, new photochromic materials and molecular data processing and storage. Herein, we report visible light responsive chiroptical switches based on tetrahedral boron coordination towards an easily accessible hydrazone ligand and optically pure BINOL. Upon instalment of a non-planar dibenzo[a,d]-cycloheptene moiety in the hydrazone ligand's lower half, the enantiopure boron complex shows major chiroptical changes in the CD read-out after visible light irradiation. The thermal isomerization barrier in these chiroptical switching systems showed to be easily adjustable by the introduction of substituents onto the olefinic bond of the cycloheptene ring, giving profound control over their thermal stability. The control over their thermal stability in combination with excellent reversibility, photochemical properties and overall robustness of the complexes makes these BINOL-derived chiroptical switches attractive candidates for usage in advanced applications, e.g. photonic materials and nanotechnology.

ROYAL SOC CHEMISTRY2022

Carbazol-phenyl-phenothiazine-based sensitizers for dye-sensitized solar cells

Yi Ding, Felix Thomas Eickemeyer, Wei Huang, Yunfei Jiao, Lukas Pfeifer, Dan Ren, Zhongjin Shen, Shaik Mohammed Zakeeruddin

Heteroaromatic units are commonly used as pi-spacers for sensitizers in dye-sensitized solar cells (DSSCs). Here, we investigated the influence of the pi-spacer on the photophysical properties, electrochemical properties and photovoltaic performance of carbazol-phenyl functionalized phenothiazine donor based organic dyes, i.e., CPPC-No (without a pi-spacer), CPPC-Th (thiophene as the pi-spacer), CPPC-Fu (furane as the pi-spacer), CPPC-Ph (phenyl as the pi-spacer) and CPPC-Py (pyridine as the pi-spacer). The solar to electric power conversion efficiency (PCE) achieved with these dyes strongly depends on the type of pi-spacer, increasing in the order of CPPC-Ph < No < Py < Th < Fu. The width of the absorption band and the photocurrent density increased with the electron richness of the pi-spacer. Theoretical calculations indicated that the planar molecular configuration of CPPC-Fu promotes the intramolecular charge transfer process. As a result, the CPPC-Fu based device showed a PCE of 7.4% under one sunlight illumination. The dyes using thiophene and pyridine as pi-spacers showed slightly lower performance, however, still significantly higher than the PCE achieved with the control compound lacking a pi-spacer. By contrast, introducing a phenyl group as the pi-spacer led to a decrease in device efficiency. These results give deeper insight into the effect of different pi-spacers on DSSC performance, showing the importance of molecular engineering in developing high efficiency organic dyes.

ROYAL SOC CHEMISTRY2021