The central role of the metal ion for photoactivity: Zn- Ni-Mabiq.

Photoredox catalysts are integral components of artificial photosystems, and have recently emerged as powerful tools for catalysing numerous organic reactions. However, the development of inexpensive and efficient earth-abundant photoredox catalysts remains a challenge. We here present the photochemical and photophysical properties of a Ni-Mabiq catalyst ([Ni(Mabiq)]OTf (); Mabiq = 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2-biquinazolino)-[15]-1,3,5,8,10,14-hexaene1,3,7,9,11,14-N)-and of a Zn-containing analogue ([Zn(Mabiq)OTf] ())-using steady state and time resolved optical spectroscopy, time-dependent density functional theory (TDDFT) calculations, and reactivity studies.

Tuning the Ground and Excited State Dynamics of Hemithioindigo Molecular Motors by Changing Substituents.

Efficiency and performance of light triggered molecular motors are crucial features that need to be mechanistically understood to improve the performance and enable conscious property tailoring for specific applications. In this work, three different hemithioindigo-based molecular motors are investigated and all four steps in their complete unidirectional rotation are unraveled fully quantitatively. Transient absorption spectroscopy across twelve orders of magnitude in time is used to probe the fs nuclear motions up to the ms thermal kinetics, covering the timeframe of the whole motor rotation.

Icelike Vibrational Properties of Strong Hydrogen Bonds in Hydrated Lithium Nitrate.

The hydrogen bond network accounts for many of the extraordinary physical properties of liquid water and ice. Its vibrational dynamics are quite complex in their entirety but can be accessed in detail by investigating small groups of only a few water molecules. Here, aqueous salt hydrates turned out to be an exceptional model system for water molecules arranged in well-defined geometrical structures that can be accessed by means of femtosecond spectroscopy of the OH stretching vibration.

Space- and time-resolved UV-to-NIR surface spectroscopy and 2D nanoscopy at 1 MHz repetition rate.

We describe a setup for time-resolved photoemission electron microscopy with aberration correction enabling 3 nm spatial resolution and sub-20 fs temporal resolution. The latter is realized by our development of a widely tunable (215-970 nm) noncollinear optical parametric amplifier (NOPA) at 1 MHz repetition rate. We discuss several exemplary applications.

Octave-spanning single-cycle middle-infrared generation through optical parametric amplification in LiGaS.

We report the generation of extremely broadband and inherently phase-locked mid-infrared pulses covering the 5 to 11 µm region. The concept is based on two stages of optical parametric amplification starting from a 270-fs Yb:KGW laser source. A continuum seeded, second harmonic pumped pre-amplifier in β-BaBO (BBO) produces tailored broadband near-infrared pulses that are subsequently mixed with the fundamental pump pulses in LiGaS (LGS) for mid-infrared generation and amplification.

Excited-state dynamics of a molecular dyad with two orthogonally-oriented fluorophores.

The excited-state dynamics of a T-shaped bichromophoric molecule, consisting of two strong fluorophores, diphenyloxazole and diphenylpyrazoline, directly linked in an orthogonal geometry, was investigated. Despite the weak coupling ensured by this geometry and confirmed by the electronic absorption spectra, this dyad exhibits only weak fluorescence in both apolar and polar solvents, with fluorescence lifetimes ranging from 200 ps in CHX to 10 ps in ACN. Ultrafast spectroscopic measurements reveal that the fluorescence quenching in polar solvents is due to the population of a charge-separated state.

10 W CEP-stable few-cycle source at 2 µm with 100 kHz repetition rate.

We developed a high repetition rate optical parametric chirped-pulse amplification (OPCPA) laser system based on fiber-laser-seeded Innoslab to generate few-cycle pulses around 2 µm with passively stable carrier-envelope phase (CEP) by difference frequency generation (DFG). Incorporating a piezo mirror before the DFG stage permits rapid CEP control. The OPCPA system is seeded by a stable supercontinuum generated in bulk material with the picosecond Innoslab pulses.

Visible-Light-Driven "On"/"Off" Photochromism of a Polyoxometalate Diarylethene Coordination Complex.

Herein we report the first photochromic polyoxometalate (POM)-based diarylethene (DAE) coordination complex, prepared by ligation of two cobalt(III)-incorporated borotungstates [BWOCo] with the ditopic pyridyl-containing diarylethene (CHNFS). The solution-state composition, structure, and stability of the assembly were probed using H and F nuclear magnetic resonance spectroscopy (NMR), electrospray ionization quadrupolar time-of-flight mass spectrometry (ESI-QTOF-MS), ultraviolet-visible spectroscopy (UV-vis), and small-angle X-ray scattering (SAXS), revealing that the complex self-organizes to adopt a molecular dumbbell structure due to electrostatic and steric considerations. This conformation is a prerequisite for the photocyclization reaction.

Complete Mechanism of Hemithioindigo Motor Rotation.

Hemithioindigo-based molecular motors are powered by nondamaging visible light and provide very fast directional rotations at ambient conditions. Their ground state energy profile has been probed in detail, but the crucial excited state processes are completely unknown so far. In addition, very fast processes in the ground state are also still elusive to date and thus knowledge of the whole operational mechanism remains to a large extent in the dark.

Dynamics of the OH stretching mode in crystalline Ba(ClO)·3HO.

The vibrational dynamics of the OH stretching mode in Ba(ClO) trihydrate are investigated by means of femtosecond infrared spectroscopy. The sample offers plane cyclic water trimers in the solid phase that feature virtually no hydrogen bond interaction between the water molecules. Selective excitation of the symmetric and asymmetric stretching leads to fast population redistribution, while simultaneous excitation yields quantum beats, which are monitored via a combination tone that dominates the overtone spectrum.

Phase-locked multi-terahertz electric fields exceeding 13 MV/cm at a 190 kHz repetition rate.

We demonstrate a compact source of energetic and phase-locked multi-terahertz pulses at a repetition rate of 190 kHz. Difference frequency mixing of the fundamental output of an Yb:KGW amplifier with the idler of an optical parametric amplifier in GaSe and LiGaS crystals yields a passively phase-locked train of waveforms tunable between 12 and 42 THz. The shortest multi-terahertz pulses contain 1.

Discrete dispersion scanning as a simple method for broadband femtosecond pulse characterization.

A simple and easy to implement technique for femtosecond pulse characterization is proposed and experimentally verified. It is based on the introduction of a known amount of dispersion (by controlling the number of passes through dispersive material) and subsequent recording of the spectral positions of second harmonic peaks obtained in a non-linear crystal. Such dependence allows for direct retrieval of the pulse spectral phase.

Hole-transfer induced energy transfer in perylene diimide dyads with a donor-spacer-acceptor motif.

We investigate the photoinduced dynamics of perylene diimide dyads based on a donor-spacer-acceptor motif with polyyne spacers of varying length by pump-probe spectroscopy, time resolved fluorescence, chemical variation and quantum chemistry. While the dyads with pyridine based polyyne spacers undergo energy transfer with near-unity quantum efficiency, in the dyads with phenyl based polyyne spacers the energy transfer efficiency drops below 50%. This suggests the presence of a competing electron transfer process from the spacer to the energy donor as the excitation sink.

Vibronic energy relaxation approach highlighting deactivation pathways in carotenoids.

Energy relaxation between two electronic states of a molecule is mediated by a set of relevant vibrational states. We describe this fundamental process in a fully quantum mechanical framework based on first principles. This approach explains population transfer rates as well as describes the entire transient absorption signal as vibronic transitions between electronic states.

Highly Selective Relaxation of the OH Stretching Overtones in Isolated HDO Molecules Observed by Infrared Pump-Repump-Probe Spectroscopy.

A quantitative investigation of the relaxation dynamics of higher-lying vibrational states is afforded by a novel method of infrared pump-repump-probe spectroscopy. The technique is used to study the dynamics of OH stretching overtones in NaClO4·HDO monohydrate. We observe a continuous decrease of the energy separation for the first four states, i.

Photochemical formation of intricarene.

Sunlight is the ultimate driver of biosynthesis but photochemical steps late in biosynthetic pathways are very rare. They appear to play a role in the formation of certain furanocembranoids isolated from Caribbean corals. One of these compounds, intricarene, has been suspected to arise from an intramolecular 1,3-dipolar cycloaddition involving an oxidopyrylium.

Sub-20 fs μJ-energy pulses tunable down to the near-UV from a 1 MHz Yb-fiber laser system.

Optical parametric amplifiers render widely tunable ultrashort pulses, but for full spectral coverage, complex mixing schemes are needed. In particular, the blue and near-UV part of the spectrum is not directly reached with the 800 nm pump from Ti:sapphire systems or the 1030 nm pump of Yb-based lasers. We combine third harmonic pumping at 343 nm with seeding by a second harmonic (SH) pumped continuum to tune a noncollinear optical parametric amplifier down to 395 nm.

A novel setup for femtosecond pump-repump-probe IR spectroscopy with few cycle CEP stable pulses.

We present a three-color mid-IR setup for vibrational pump-repump-probe experiments with a temporal resolution well below 100 fs and a freely selectable spectral resolution of 20 to 360 cm(-1) for the pump and repump. The usable probe range without optical realignment is 900 cm(-1). The experimental design employed is greatly simplified compared to the widely used setups, highly robust and includes a novel means for generation of tunable few-cycle pulses with stable carrier-envelope phase.

Conformational control of benzophenone-sensitized charge transfer in dinucleotides.

Charge transfer in DNA cannot be understood without addressing the complex conformational flexibility, which occurs on a wide range of timescales. In order to reduce this complexity four dinucleotide models 1X consisting of benzophenone linked by a phosphodiester to one of the natural nucleosides X = A, G, T, C were studied in water and methanol. The theoretical work focuses on the dynamics and electronic structure of 1G.

Ultrafast Dynamics of meso-Tetraphenylmetalloporphyrins: The Role of Dark States.

Studying the relaxation pathways of porphyrins and related structures upon light absorption is crucial to understand the fundamental processes of light harvesting in biosystems and many applications. Herein, we show by means of transient absorption studies, following Q- and Soret-band excitation, and ab initio calculations on meso-tetraphenylporphyrinato magnesium(II) (MgTPP) and meso-tetraphenylporphyrinato cadmium(II) (CdTPP) that electronic relaxation following Soret-band excitation of porphyrins with a heavy central atom is mediated by a hitherto disregarded dark state. This accounts for an increased rate of internal conversion.

Electronic transient spectroscopy from the deep UV to the NIR: unambiguous disentanglement of complex processes.

Complex multi-stage relaxation and reaction pathways after the optical excitation of molecules makes the disentanglement of the underlying mechanisms challenging. We present four examples that a new transient spectrometer with excitation fully tunable from the deep UV to the IR and 225 to 1700 nm probing allows for an analysis with greatly reduced ambiguity. The temporal resolution of about 50 fs allows us to resolve all relevant processes.

LED based NMR illumination device for mechanistic studies on photochemical reactions--versatile and simple, yet surprisingly powerful.

An LED based illumination device for mechanistic studies on photochemical reactions by means of NMR spectroscopy is presented. The LEDs are directly switched by the NMR spectrometer with the help of a one-stage electronic circuit. This allows for continuous or alternatively pulsed operation of the LEDs.

Intramolecular [2+2] photocycloaddition of 3- and 4-(but-3-enyl)oxyquinolones: influence of the alkene substitution pattern, photophysical studies, and enantioselective catalysis by a chiral sensitizer.

The intramolecular [2+2] photocycloaddition of four 4-(but-3-enyl)oxyquinolones (substitution pattern at the terminal alkene carbon atom: CH2, Z-CHEt, E-CHEt, CMe2) and two 3-(but-3-enyl)oxyquinolones (substitution pattern: CH2, CMe2) was studied. Upon direct irradiation at λ=300 nm, the respective cyclobutane products were formed in high yields (83-95 %) and for symmetrically substituted substrates with complete diastereoselectivity. Substrates with a Z- or E-substituted terminal double bond showed a stereoconvergent reaction course leading to mixtures of regio- and diastereomers with almost identical composition.

A comprehensive microscopic picture of the benzhydryl radical and cation photogeneration and interconversion through electron transfer.

Bond cleavage and bond formation are central to organic chemistry. Carbocations play a key role in our understanding of nucleophilic substitution reactions that involve both processes. The precise understanding of the mechanism and dynamics of the photogeneration of carbocations and carbon radicals is therefore an important quest.

Seeding of picosecond and femtosecond optical parametric amplifiers by weak single mode continuous lasers.

Optical parametric amplifiers are typically seeded with either parametric superfluorescence or broadband continuum pulses. We show both with picosecond and femtosecond pump pulses, that single longitudinal mode cw lasers with mW power can be well used to generate nearly Fourier-transform-limited output pulses. The 532 nm pumped picosecond system is seeded in the near infrared and fully tunable from 1260 to 1630 nm.