Anti-Kasha Conformational Photoisomerization of a Heteroleptic Dithiolene Metal Complex Revealed by Ultrafast Spectroscopy

We investigated the anti-Kasha photochemistry and anti-Kasha emission of d8-metal donor-acceptor dithiolene with femtosecond UV-vis transient absorption spectroscopy and molecular modeling. Experimentally, we found a lifetime of 1.4 ps for higher excited states, which is exceptionally long when compared to typical values for internal conversion (IC) (10 s of fs or less). Consequently, a substantial emission originates from the second excited state. Molecular modeling suggests this to be a consequence of the spatially separated molecular orbitals of the first and second excited states, which gives a charge transfer character to the IC. More surprisingly, we found that the inherent flexibility of the molecule allows the metal complex to access different configurations depending on the photoexcited state. We believe that this unique manifestation of anti-Kasha photoinduced conformational isomerization is facilitated by the exceptionally long lifetime of the second excited state

Ultrafast spectroscopic investigation on fluorescent carbon nanodots: the role of passivation

Disentangling the respective roles of the surface and core structures in the photocycle of carbon nanodots is a critical open problem in carbon nanoscience. While the need of passivating carbon dot surfaces to obtain efficiently emitting nanoparticles is very well-known in the literature, it is unclear if passivation introduces entirely new surface emitting states, or if it stabilizes existing states making them fluorescent. In this multi-technique femtosecond spectroscopy study, the relaxation dynamics of non-luminescent (non-passivated) carbon dots are directly compared with their luminescent (passivated) counterparts. Non-passivated dots are found to host emissive states, albeit very short-lived and practically incapable of steady-state fluorescence. In contrast, the passivation procedure gives birth to a distinctive new manifold of emitting states, localized on the surface of the dots, and capable of intense, tunable, long-lived fluorescence. It turns out that these surface states are instantaneously populated by photo-excitation, and their subsequent dynamics are entirely independent of core electronic transitions. The experiments reveal the lack of any crosstalk between core- and surface states, at least for certain common types of carbon dots, and open a new perspective on the mechanisms by which surface passivation governs the fluorescence properties of these nanoparticles

Anti-Kasha Photophysics and Photochemistry in Pt-dithiolene Complexes Investigated with Ultrafast Transient Absorption

Metal-dithiolene complexes with d8-square planar structure and non-innocent ligands show outstanding hyperpolarizability and nonlinear optical behavior due to highly delocalized frontier electrons, making them interesting for photovoltaics, visual and sensing technologies. They can potentially act as charge transfer (CT) relays for artificial photocatalyzers, controllable by external stimuli as light, temperature, solvent polarity, etc. For instance complexes containing quinoxdt ligands show proton-switchable properties in acidic solutions. Surprisingly, quinoxdt complexes have additionally a photophysical response that markedly dependents on the excitation wavelength (anti-Kasha behavior). Systems with such an uncommon behavior have raised more and more interest because of the possibility to conceive multi-response molecular devices or to explore novel photochemical routes. Such a behavior originates from a competition between the functional process in the upper photo-excited state and internal conversion (IC) towards the lowest excited state. Therefore femtosecond transient absorption is ideal to characterize the anti-Kasha process with the perspective to optimize its performance. We elucidated the origin of the anti-Kasha behavior both in homoleptic and heteroleptic quinoxdt complexes, which stems from a neat spatial separation between the molecular orbitals of the excited states localized on the quinoxdt moiety. This electronic arrangement gives a CT character to the IC slowing down the process. We also discuss the role of such an unusually long lifetime of the photo-excited higher state on the functional processes characterizing the two investigated complexes, namely photocatalytic H2 production and photo-induced chemiluminescence, respectively

The interaction of photoexcited carbon nanodots with metal ions disclosed down to the femtosecond scale

Fluorescent carbon nanodots are a novel family of carbon-based nanoscale materials endowed with an outstanding combination of properties that make them very appealing for applications in nanosensing, photonics, solar energy harvesting and photocatalysis. One of the remarkable properties of carbon dots is their strong sensitivity to the local environment, especially to metal ions in solution. These interactions provide a testing ground for their marked photochemical properties, highlighted by many studies, and frequently driven by charge transfer events. Here we combine several optical techniques, down to femtosecond time resolution, to understand the interplay between carbon nanodots and aqueous metal ions such as Cu²⁺ and Zn²⁺. We find that copper inhibits the fluorescence of carbon dots through static and diffusional quenching mechanisms, and our measurements allow discriminating between the two. Ultrafast optical methods are then used to address the dynamics of copper-dot complexes, wherein static quenching takes place, and unveil the underlying complexity of their photocycle. We propose an initial increase of electronic charge on the surface of the dot, upon photo-excitation, followed by a partial electron transfer to the nearby ion, with 0.2 ps and 1.9 ps time constants, and finally a very fast (≪1 ps) non-radiative electron–hole recombination which brings the system back to the ground state. Notably, we find that the electron transfer stage is governed by an ultrafast water rearrangement around photo-excited dots, pointing out the key role of solvent interactions in the photo-physics of these systems

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu–C and Cu–P bonds represents an underexplored type of luminophore. To investigate the charge transfer and structural rearrangements in this material, we apply complementary pump-probe X-ray techniques: absorption, emission, and scattering including pump-probe measurements at the X-ray free-electron laser SwissFEL. We find that the excitation leads to charge movement from C- and P- coordinated Cu sites and from the phosphorus atoms to phenyl rings; the Cu core slightly rearranges with 0.05 Å increase of the shortest Cu–Cu distance. The use of a Cu cluster bonded to the ligands through C and P atoms is an efficient way to keep structural rigidity of luminophores. Obtained data can be used to verify computational methods for the development of luminophores.ISSN:2041-172