Ultrafast Photodynamics Research Articles

A Competition among Three Ultrafast Photoinduced Events in Thiotropolone: Internal Conversion vs Intersystem Crossing vs ESIPT.

Gas phase excited-state quantum wavepacket dynamics simulations of the thiotropolone demonstrate the ultrafast triplet formation upon photoexcitation to the dipole-allowed S2 state. The dominant relaxation pathway of the S2-T4 intersystem crossing, facilitated by the strong spin-orbit coupling and narrow energy gap, competes with the S2 to S1/S3 internal conversion. The wavepacket populated in T4 via the former pathway decays to lower triplet states. Computed potential energy profiles suggest proton transfer via S2, which might compete with internal conversion and intersystem crossing. The nonadiabatic population transfer from the S2 to S1/S3 states enables proton transfer via the latter states, resulting in multiple proton transfer pathways. Experimental investigations are necessary to shed light on the complex ultrafast photodynamics of thiotropolone.

Revealing the Importance of Hole Transfer: Boosting Photocatalytic Hydrogen Evolution by Delicate Modulation of Photogenerated Holes

Photocatalytic hydrogen evolution (PHE) has gained massive attention for the development of renewable resources. Currently, prominent and stable PHE is still restricted by the limited utilization of photocatalytic charge carriers, especially holes, of which the transfer rate is approximately two to three orders of magnitude slower than that of electrons. Although it is widely accepted that surface holes can be consumed by electron donors, the rational design of photocatalysts to speed up hole transfer and understand the ultrafast photodynamics as well as the exploration of the effect of oxidation products is still highly urgent. Herein, cadmium sulfide (CdS), as the model photocatalyst, is investigated for prominent PHE based on hole modulation strategies. To accelerate the surface reaction, H2S-saturated Na2S&Na2SO3 solution, which outperforms traditional hole scavengers, is selected to remove the holes accumulating on the photocatalyst surface, while the oxidative cocatalyst palladium sulfide (PdS) is simultaneously impregnated on CdS to optimize the hole transfer process. Evidenced by femtosecond transient absorption spectroscopy (TAS) and band structure analysis, the ultrafast process (1–5 ps) highly related with hole transfer from CdS to PdS is proved in the CdS/PdS composite. More importantly, density functional theory (DFT) calculation suggests that the hole accumulation site (PdS) is also the oxidation active site where the active species (HS*) adsorbs on. Finally, the oxidation product composition is analyzed through Fourier transform infrared (FTIR) spectroscopy, which indicates that the colorless and value-added product S2O32– protects the photocatalyst from the light shielding effect. Contributed by factors mentioned above, improved PHE efficiency (∼145.9 mmol·g–1·h–1) is achieved on the CdS/PdS composite.

Ion-Pair Formation in n-Butyl Bromide through 5p Ryberg State Predissociation.

The ultrafast photodynamics of n-butyl bromide are explored with femtosecond time-resolved mass spectrometry. Absorption of two UV (400 nm) pump photons induces the direct dissociation of the C-Br bond from the A state within 160 fs. Absorption of three UV pump photons excites the molecule into the 5p Rydberg state which undergoes several relaxation pathways including to the ion-pair state. Relaxation to the ion-pair state is tracked through the transient of the C4H9+ fragment and suggests an E state lifetime of 10.8 ± 0.5 ps, in close agreement with the tunneling time of smaller molecules. Predissociation from the 5p Rydberg states leads to the β-elimination of H-Br and formation of C4H8+ within 3.0 ± 0.25 ps. A portion of the excited parent molecule avoids the ion-pair formation and instead relaxes through the Rydberg excited state manifold into the D state within 30.2 ± 0.21 ps.

Ultrafast Dynamics of Photoinduced Electron Transfer in Bay-Aryl-Substituted Perylene Diimide Derivatives.

Blends of donors and acceptors have been widely used in bulk-heterojunction solar cells to have exciton formation and charge separation by photoinduced electron transfer (PET). In this work, we have synthesized perylene diimide (PDI)-based materials having different aryl substituents at the bay positions (4-Anisyl-PDI, CBZ-N-Ph-PDI, and 4-Pyridyl-PDI) to understand the excited-state dynamics of electron transfer. The detailed photophysics was studied using steady-state as well as ultrafast dynamics of the excited states in different solvents. CBZ-N-Ph-PDI showed tremendous effects of the solvent on the electronic properties compared with the other two derivatives. The emission quantum yield of CBZ-N-Ph-PDI decreases drastically in dichloromethane and other polar solvents, indicating strong electron transfer. DFT calculations showed that in CBZ-N-Ph-PDI the HOMO is centered mostly on the N-phenylcarbazole and the LUMO is on the electron-poor PDI moieties. In addition, the energy levels of the HOMO and HOMO-1 in CBZ-N-Ph-PDI are estimated to be identical. The free energy change for charge separation (ΔGCS) was calculated using electrochemical and photophysical data and found to be negative for CBZ-N-Ph-PDI. The ground- and excited-state dipole moment ratios suggest that the excited state of 4-Pyridyl-PDI (1.90) is less polar than that of 4-Anisyl-PDI (3.67), which provides an idea of the lower possibility of charge separation in 4-Anisyl-PDI and 4-Pyridyl-PDI. Ultrafast photodynamics studies of 4-Anisyl-PDI, CBZ-N-Ph-PDI, and 4-Pyridyl-PDI showed fast electron transfer only in CBZ-N-Ph-PDI and not in the other PDI derivatives. It was also observed that electron transfer is faster in DCM and THF than in toluene. Ultrafast dynamics studies showed the presence of an equilibrium between electron transfer and decay from the singlet excited state. Ultrafast studies also showed the features of the N-phenylcarbazole cation and PDI anion, further confirming the intramolecular electron transfer in CBZ-N-Ph-PDI.

Unifying Perspective of the Ultrafast Photodynamics of Orange Carotenoid Proteins from Synechocystis: Peril of High-Power Excitation, Existence of Different S* States, and Influence of Tagging.

A substantial number of Orange Carotenoid Protein (OCP) studies have aimed to describe the evolution of singlet excited states leading to the formation of a photoactivated form, OCPR. The most recent one suggests that 3 ps-lived excited states are formed after the sub-100 fs decay of the initial S2 state. The S* state, which has the longest reported lifetime of a few to tens of picoseconds, is considered to be the precursor of the first red photoproduct P1. Here, we report the ultrafast photodynamics of the OCP from Synechocystis PCC 6803 carried out using visible–near infrared femtosecond time-resolved absorption spectroscopy as a function of the excitation pulse power and wavelength. We found that a carotenoid radical cation can form even at relatively low excitation power, obscuring the determination of photoactivation yields for P1. Moreover, the comparison of green (540 nm) and blue (470 nm) excitations revealed the existence of an hitherto uncharacterized excited state, denoted as S∼, living a few tens of picoseconds and formed only upon 470 nm excitation. Because neither the P1 quantum yield nor the photoactivation speed over hundreds of seconds vary under green and blue continuous irradiation, this S∼ species is unlikely to be involved in the photoactivation mechanism leading to OCPR. We also addressed the effect of His-tagging at the N- or C-termini on the excited-state photophysical properties. Differences in spectral signatures and lifetimes of the different excited states were observed at a variance with the usual assumption that His-tagging hardly influences protein dynamics and function. Altogether our results advocate for the careful consideration of the excitation power and His-tag position when comparing the photoactivation of different OCP variants and beg to revisit the notion that S* is the precursor of photoactivated OCPR.

Ultrafast transient absorption spectroelectrochemistry: femtosecond to nanosecond excited-state relaxation dynamics of the individual components of an anthraquinone redox couple.

Many photoactivated processes involve a change in oxidation state during the reaction pathway and formation of highly reactive photoactivated species. Isolating these reactive species and studying their early-stage femtosecond to nanosecond (fs–ns) photodynamics can be challenging. Here we introduce a combined ultrafast transient absorption-spectroelectrochemistry (TA-SEC) approach using freestanding boron doped diamond (BDD) mesh electrodes, which also extends the time domain of conventional spectrochemical measurements. The BDD electrodes offer a wide solvent window, low background currents, and a tuneable mesh size which minimises light scattering from the electrode itself. Importantly, reactive intermediates are generated electrochemically, via oxidation/reduction of the starting stable species, enabling their dynamic interrogation using ultrafast TA-SEC, through which the early stages of the photoinduced relaxation mechanisms are elucidated. As a model system, we investigate the ultrafast spectroscopy of both anthraquinone-2-sulfonate (AQS) and its less stable counterpart, anthrahydroquinone-2-sulfonate (AH2QS). This is achieved by generating AH2QS in situ from AQS via electrochemical means, whilst simultaneously probing the associated early-stage photoinduced dynamical processes. Using this approach we unravel the relaxation mechanisms occurring in the first 2.5 ns, following absorption of ultraviolet radiation; for AQS as an extension to previous studies, and for the first time for AH2QS. AQS relaxation occurs via formation of triplet states, with some of these states interacting with the buffered solution to form a transient species within approximately 600 ps. In contrast, all AH2QS undergoes excited-state single proton transfer with the buffered solution, resulting in formation of ground state AHQS− within approximately 150 ps.

Ab Initio Quasiclassical Simulation of Femtosecond Time-Resolved Two-Dimensional Electronic Spectra of Pyrazine.

Two-dimensional (2D) electronic spectroscopy is a powerful nonlinear technique which provides spectroscopic information on two frequency axes as well as dynamical information as a function of the so-called waiting time. Herein, an ab initio theoretical framework for the simulation of electronic 2D spectra has been developed. The method is based on the classical approximation to the doorway-window representation of three-pulse photon-echo signals and the description of nuclear motion by classical trajectories. Nonadiabatic effects are taken into account by a trajectory surface-hopping algorithm. 2D electronic spectra were simulated with ab initio on-the-fly trajectory calculations using the ADC(2) electronic-structure method for the pyrazine molecule, which is a benchmark system for ultrafast radiationless decay through conical intersections. It is demonstrated that 2D spectroscopy with subfemtosecond UV pulses can provide unprecedented detailed information on the ultrafast photodynamics of polyatomic molecules.

Ultrafast Photoconversion Dynamics of the Knotless Phytochrome SynCph2.

The family of phytochrome photoreceptors contains proteins with different domain architectures and spectral properties. Knotless phytochromes are one of the three main subgroups classified by their distinct lack of the PAS domain in their photosensory core module, which is in contrast to the canonical PAS-GAF-PHY array. Despite intensive research on the ultrafast photodynamics of phytochromes, little is known about the primary kinetics in knotless phytochromes. Here, we present the ultrafast Pr ⇆ Pfr photodynamics of SynCph2, the best-known knotless phytochrome. Our results show that the excited state lifetime of Pr* (~200 ps) is similar to bacteriophytochromes, but much longer than in most canonical phytochromes. We assign the slow Pr* kinetics to relaxation processes of the chromophore-binding pocket that controls the bilin chromophore’s isomerization step. The Pfr photoconversion dynamics starts with a faster excited state relaxation than in canonical phytochromes, but, despite the differences in the respective domain architectures, proceeds via similar ground state intermediate steps up to Meta-F. Based on our observations, we propose that the kinetic features and overall dynamics of the ultrafast photoreaction are determined to a great extent by the geometrical context (i.e., available space and flexibility) within the binding pocket, while the general reaction steps following the photoexcitation are most likely conserved among the red/far-red phytochromes.

Ultrafast Dynamics and Estimation of Singlet Exciton Diffusion Parameters for Nanoaggregates of peri and bay Anisyl Perylene

The correlation between molecular structure and its photophysics is well reported, and organic chemistry is blessed with the freedom of substitution to obtain the desired photophysical property, suitable to control the functional aspects of materials. Despite the fact that the photodynamics of perylene has been studied in depth, its bay and peri aryl-substituted derivatives have not been studied to that extent. Herein, the ultrafast photodynamics of two anisyl perylene derivatives (peri-OCH3 and bay-OCH3) is presented. Isomers of anisyl perylene were designed to study the positional effect of substitution on their molecular packing and excited-state photophysics. The fluorescence spectra of nanoaggregates of peri-OCH3 showed excimer formation, while monomer emission is dominated in bay-OCH3. These features are consistent with the solid-state α-phase and β-phase of perylene, respectively, which are grown in a very precise and controlled manner. Excited-state dynamics studies show that in peri-OCH3, the monomeric free excitons undergo a relatively faster decay to populate the self-trapped monomeric excitonic state and E-state. In bay-OCH3, the contribution of emission from the Y-state and E-state is much less. The molecular structure alteration and different packing are also observed to have an impact on the exciton diffusion rate. The bay-OCH3 isomer is observed to have an almost-double diffusion length, which is attributed to the slightly faster diffusion and longer lifetime of free excitons. The present report indicates the structural modulation effect on the exciton-to-excimer transition dynamics and exciton diffusion properties, which can be beneficial in designing perylene-based materials for organic electronics.

Determining the photostability of avobenzone in sunscreen formulation models using ultrafast spectroscopy.

Avobenzone is an ultraviolet (UV) filter that is often included in sunscreen formulations despite its lack of photostability. Its inclusion is necessary due to few existing alternatives for photoprotection in the UVA region (320-400 nm). To better understand and predict the photostability of avobenzone, ultrafast transient electronic absorption spectroscopy (TEAS) has been used to study the effects of solvent (including emollients), concentration and skin surface temperature on its excited-state relaxation mechanism, following photoexcitation with UVA radiation (∼350 nm). Subtle differences between the excited-state lifetimes were found between the systems, but the TEAS spectral features were qualitatively the same for all solution and temperature combinations. Alongside TEAS measurements, UV filter/emollient blends containing avobenzone were irradiated using simulated solar light and their degradation tracked using steady-state UV-visible spectroscopy. Sun protection factor (SPF) and UVA protection factor (UVA-PF) assessments were also carried out on representative oil phases (higher concentration blends), which could be used to formulate oil-in-water sunscreens. It was found that there was an apparent concentration dependence on the long-term photoprotective efficacy of these mixtures, which could be linked to the ultrafast photodynamics by the presence of a ground-state bleach offset. This combination of techniques shows potential for correlating long-term behaviours (minutes to hours) of avobenzone with its ultrafast photophysics (femtoseconds to nanoseconds), bridging the gap between fundamental photophysics/photochemistry and commercial sunscreen design.

New Generation UV-A Filters: Understanding Their Photodynamics on a Human Skin Mimic.

The sparsity of efficient commercial ultraviolet-A (UV-A) filters is a major challenge toward developing effective broadband sunscreens with minimal human- and eco-toxicity. To combat this, we have designed a new class of Meldrum-based phenolic UV-A filters. We explore the ultrafast photodynamics of coumaryl Meldrum, CMe, and sinapyl Meldrum (SMe), both in an industry-standard emollient and on a synthetic skin mimic, using femtosecond transient electronic and vibrational absorption spectroscopies and computational simulations. Upon photoexcitation to the lowest excited singlet state (S1), these Meldrum-based phenolics undergo fast and efficient nonradiative decay to repopulate the electronic ground state (S0). We propose an initial ultrafast twisted intramolecular charge-transfer mechanism as these systems evolve out of the Franck-Condon region toward an S1/S0 conical intersection, followed by internal conversion to S0 and subsequent vibrational cooling. Importantly, we correlate these findings to their long-term photostability upon irradiation with a solar simulator and conclude that these molecules surpass the basic requirements of an industry-standard UV filter.

Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations.

The photochemistry of bilirubin has been extensively studied due to its importance in the phototherapy of hyperbilirubinemia. In the present work, we investigated the ultrafast photodynamics of a bilirubin dipyrrinone subunit, vinylneoxanthobilirubic acid methyl ester. The photoisomerization and photocyclization reactions of its (E) and (Z) isomers were studied using femtosecond transient absorption spectroscopy and by multireference electronic structure theory, where the nonadiabatic dynamics was modeled with a Landau-Zener surface hopping technique. The following picture has emerged from the combined theoretical and experimental approach. Upon excitation, dipyrrinone undergoes a very fast vibrational relaxation, followed by an internal conversion on a picosecond time scale. The internal conversion leads either to photoisomerization or regeneration of the starting material. Further relaxation dynamics on the order of tens of picoseconds was observed in the ground state. The nonadiabatic simulations revealed a strong conformational control of the photodynamics. The ultrafast formation of a cyclic photochemical product from a less-populated conformer of the studied subunit was predicted by our calculations. We discuss the relevance of the present finding for the photochemistry of native bilirubin. The work has also pointed to the limits of semiclassical nonadiabatic simulations for simulating longer photochemical processes, probably due to the zero-point leakage issue.

Ultrafast Photodynamics and Quantitative Evaluation of Biohybrid Photosynthetic Antenna and Reaction Center Complexes Generating Photocurrent

A functional linkage between light-harvesting and photocatalytic components is a pivotal issue for using solar energy in chemical conversions; however, this concept is far from being practically re...

Efficient Plasmon-Mediated Energy Funneling to the Surface of Au@Pt Core-Shell Nanocrystals.

The structure and ultrafast photodynamics of ∼8 nm Au@Pt core-shell nanocrystals with ultrathin (<3 atomic layers) Pt-Au alloy shells are investigated to show that they meet the design principles for efficient bimetallic plasmonic photocatalysis. Photoelectron spectra recorded at two different photon energies are used to determine the radial concentration profile of the Pt-Au shell and the electron density near the Fermi energy, which play a key role in plasmon damping and electronic and thermal conductivity. Transient absorption measurements track the flow of energy from the plasmonic core to the electronic manifold of the Pt shell and back to the lattice of the core in the form of heat. We show that strong coupling to the high density of Pt(d) electrons at the Fermi level leads to accelerated dephasing of the Au plasmon on the femtosecond time scale, electron-electron energy transfer from Au(sp) core electrons to Pt(d) shell electrons on the sub-picosecond time scale, and enhanced thermal resistance on the 50 ps time scale. Electron-electron scattering efficiently funnels hot carriers into the ultrathin catalytically active shell at the nanocrystal surface, making them available to drive chemical reactions before losing energy to the lattice via electron-phonon scattering on the 2 ps time scale. The combination of strong broadband light absorption, enhanced electromagnetic fields at the catalytic metal sites, and efficient delivery of hot carriers to the catalyst surface makes core-shell nanocrystals with plasmonic metal cores and ultrathin catalytic metal shells promising nanostructures for the realization of high-efficiency plasmonic catalysts.

Ultrafast Photodynamics of an Azopyridine-Functionalized Iron(II) Complex: Implications for the Concept of Ligand-Driven Light-Induced Spin Change.

We report on the ultrafast photodynamics of an iron(II) complex with a photoisomerizable pentadentate azo-tetrapyridylamino ligand after irradiation with ultraviolet light. The results of femtosecond transient electronic absorption spectroscopy performed on the low-spin (LS) form of the title complex show that initial excitation of the ππ* state of the azopyridine unit in the ligand at λpump = 312 nm is followed by an ultrafast intersystem crossing (ISC) that leads to the formation of a metal-centered (MC) 5T state, in competition with the intended photoswitching of the azopyridine unit. Additional measurements carried out upon excitation of the singlet metal-to-ligand charge-transfer (1MLCT) transition at λpump = 455 nm suggest that this energy transfer occurs via an MLCT state. The resulting high-spin (HS) 5T state of the complex is metastable and recovers to the LS ground state with a time constant of ∼3 ns. The implications of these observations on the ligand-driven light-induced spin change concept are discussed.

Photodynamics of [FeFe]-Hydrogenase Model Compounds with Bidentate Heterocyclic Ligands.

Two asymmetrically structured model compounds for the hydrogen-generating [Fe-Fe]-hydrogenase active site were investigated to determine the ultrafast photodynamics, structural intermediates, and photoproducts compared to more common symmetric di-iron species. The bidentate-ligand-containing compounds studied were Fe2(μ-S2C3H6)(CO)4(bipy), 1, and Fe2(μ-S2C3H6)(CO)4(phen), 2, in dilute room temperature acetonitrile solution and low-temperature 2Me-THF matrix isolation using static FTIR difference and time-resolved infrared spectroscopic methods (TRIR). Ultraviolet-visible spectra were also compared to time-dependent density functional theory (TD-DFT) to ascertain the orbital origins of long wavelength electronic absorption features. The spectroscopic evidence supports the conclusions that only a propyl-bridge flip occurs in low-temperature matrix, while early time CO ejection leads to the formation of solvated isomeric species on the 25 ps time scale in room temperature solution.

Comparison of ultrafast intense-field photodynamics in aniline and nitrobenzene: stability under amino and nitro substitution.

We report on the photoionization and photofragmentation of aniline (C6H5NH2) and nitrobenzene (C6H5NO2) under single-molecule conditions in the focus of 50 fs, 800 nm laser pulses. Ion mass spectra are recorded as a function of intensity ranging from 6 × 1012 to 3 × 1014 W cm-2. Ion yields are measured in the absence of the focal volume effect and without the need for additional deconvolution of data. We observe evidence of resonance-enhanced multiphoton ionization in aniline, in agreement with current literature. Phenyl-based ion fragments, singly-charged parent ions, and dissociative rearrangement processes are observed for both molecules. However, fragmentation in aniline is heavily suppressed in favor of parent ionization while the reverse is true for nitrobenzene, and multiply-charged parent ions are present in aniline and absent in nitrobenzene. We discuss the implications of these and other results as they relate to molecular stability against intense-field ionization and fragmentation, specifically with regards to the opposing behavior of the substituted amino and nitro functional groups.

Wavepacket insights into the photoprotection mechanism of the UV filter methyl anthranilate

Meradimate is a broad-spectrum ultraviolet absorber used as a chemical filter in commercial sunscreens. Herein, we explore the ultrafast photodynamics occurring in methyl anthranilate (precursor to Meradimate) immediately after photoexcitation with ultraviolet radiation to understand the mechanisms underpinning Meradimate photoprotection. Using time-resolved photoelectron spectroscopy, signal from the first singlet excited state of methyl anthranilate shows an oscillatory behavior, i.e., quantum beats. Our studies reveal a dependence of the observed beating frequencies on photoexcitation wavelength and photoelectron kinetic energy, unveiling the different Franck-Condon overlaps between the vibrational levels of the ground electronic, first electronic excited, and ground cationic states of methyl anthranilate. By evaluating the behavior of these beats with increasing photon energy, we find evidence for intramolecular vibrational energy redistribution on the first electronic excited state. Such energy redistribution hinders efficient relaxation of the electronic excited state, making methyl anthranilate a poor choice for an efficient, efficacious sunscreen chemical filter.

Ultrafast carbon monoxide photolysis and heme spin-crossover in myoglobin via nonadiabatic quantum dynamics

Light absorption of myoglobin triggers diatomic ligand photolysis and a spin crossover transition of iron(II) that initiate protein conformational change. The photolysis and spin crossover reactions happen concurrently on a femtosecond timescale. The microscopic origin of these reactions remains controversial. Here, we apply quantum wavepacket dynamics to elucidate the ultrafast photochemical mechanism for a heme–carbon monoxide (heme–CO) complex. We observe coherent oscillations of the Fe–CO bond distance with a period of 42 fs and an amplitude of ∼1 Å. These nuclear motions induce pronounced geometric reorganization, which makes the CO dissociation irreversible. The reaction is initially dominated by symmetry breaking vibrations inducing an electron transfer from porphyrin to iron. Subsequently, the wavepacket relaxes to the triplet manifold in ∼75 fs and to the quintet manifold in ∼430 fs. Our results highlight the central role of nuclear vibrations at the origin of the ultrafast photodynamics of organometallic complexes.

Photodynamics and Luminescence of Mono- and Tri-Nuclear Lanthanide Complexes in the Gas Phase and in Solution.

Lanthanide ions (DyIII , EuIII ) are stabilized by coordination with two Schiff base ligands in compounds [Dy{H3 L}2 ](NO3 )(EtOH)(H2 O)8 (1) and [Eu{H3 L}2 ](NO3 )(H2 O)8 (3) (H4 L, 2,2'-{[(2-aminoethyl)imino]bis[2,1-ethanediyl-nitriloethylidyne]}bis-2-hydroxy-benzoic acid). The latter is reported here for the first time. Both luminescence and ultrafast photodynamics after photoexcitation via a ligand absorption band (∼400 nm) have been studied. In solution, only the [Eu{H3 L}2 ]+ ([3]+ ) complex displays the typical lanthanide emission lines, whereas in gas phase both, [Dy{H3 L}2 ]+ ([1]+ ) and [3]+ , show their corresponding transitions depending on excitation energy. The ultrafast excited state dynamics, obtained in gas phase and in solution, are assigned to excited state intramolecular proton transfer processes in the ligands. The antenna ligand moiety of these complexes provides pockets for stabilization of two MnII ions so that we additionally investigated the photophysical behavior of the corresponding tri-nuclear (NHEt3 )2 [Ln{MnL}2 ](ClO4 )(H2 O)2 (Ln=DyIII , EuIII ) compounds (2, 4). Interestingly, the related complexes do not show lanthanide emission, neither in solution nor in gas phase. Transient data in solution and gas phase suggests an efficient quenching of the ligand's electronically excited state by strong interaction with the MnII ions. This effect could possibly be developed further into a design principle for luminescence-based sensing devices for metal cations.