Fs Transient Absorption Spectroscopy Research Articles

Control of electronic and exchange coupling by bridge substituents in donor acceptor triads with triptycene bridges.

A series of triads, consisting of a triarylamine electron donor and a perylene diimide electron acceptor which were attached to two different wings of a triptycene bridging unit, was investigated concerning the dynamics of photoinduced charge separation and charge recombination processes with a particular focus on the involved spin-chemical aspects. Attaching electron-donating or electron-withdrawing substituents to the third wing of the triptycene bridge allowed tuning the electron transfer processes. These processes were investigated via fs-transient absorption spectroscopy and ns-transient absorption spectroscopy in an external magnetic field. The resulting magnetic field-dependent decay dynamics were analysed and modelled using the stochastic Liouville equation which yielded rate constants for the charge recombination and the exchange energy. In combination with a diabatic rate theory and Anderson's perturbative treatment of the exchange energy, these data gave a complete set of rate constants for charge separation and charge recombination from which the diverse electronic couplings between the involved states were derived. These couplings depend linearly on the inverse energy of virtual triptycene bridge states which allows tuning the electron transfer dynamics by modifying the triptycene bridge.

The Effect of Imide Substituents on the Excited State Properties of Perylene Diimide Derivatives

Solid state optical properties of fluorescent materials are important for many optical and electronic photonic devices such as organic light emitting diodes, frequency down-converters or luminescent solar concentrators. Perylene diimides (PDIs) represent one of the most popular organic semiconductors which find application in those phonic device applications. In this study, photophysical properties of two dibrominated PDI (DiBrPDIs), one of which contains a branched alkyl chain (2-ethylhexyl, 2-EH) and the other has an aromatic substituent (diisopropylphenyl, DIA) at the imide positions are comparatively studied. Besides their absorption and photoluminescence, lifetime and photoluminescence quantum yield (PLQY), photoinduced absorption properties (PIA) were also examined by fs-transient absorption spectroscopy. Due to their the same π conjugated system, DiBrPDI-DIA and DiBrPDI-2EH exhibited identical absorption and photoluminescence (PL) spectra in solution phase (λabs:527 nm and λPL:552 nm). However, in their film phases which were prepared at the same conditions, DiBrPDI-DIA (λPL-DIA:596 nm; PLQY:73.4%) presented a shorter PL wavelength with a higher PLQY than that of DiBrPDI-2EH (λPL-2EH:649 nm; PLQY:36.7%). 3-D investigations performed by using Chem3D pro software addressed the higher intermolecular distance between the perylene rings induced by the bulky DIA groups, as the main reason of this difference.

Polariton Dynamics in Two-Dimensional Ruddlesden-Popper Perovskites Strongly Coupled with Plasmonic Lattices.

Strong coupling between light and matter can produce hybrid eigenstates known as exciton-polaritons. Although polariton dynamics are important photophysical properties, the relaxation pathways of polaritons in different coupling regimes have seen limited attention. This paper reports the dynamics of hybridized states from 2D Ruddlesden-Popper perovskites coupled to plasmonic nanoparticle lattices. The open cavity architecture of Al lattices enables the coupling strength to be modulated by varying either the lead halide perovskite film thickness or the superstrate refractive index. Both experiments and finite-difference time-domain simulations of the optical dispersion diagrams showed avoided crossings that are a signature of strong coupling. Our analytical model also elucidated the correlation between the exciton/plasmon mixing ratio and polariton coupling strength. Using fs-transient absorption spectroscopy, we found that both the upper and lower polaritons have shorter lifetimes than the excitons and that polaritons can show faster excited-state dynamics when they have access to additional energy transfer channels.

Structure and Excitation Dynamics of β-Carotene Aggregates in Cetyltrimethylammonium Bromide Micelle

The β-carotene(β-Car) aggregate was prepared by self-assembly in cetyltrimethylammonium bromide (CTAB) micelle. The ground state absorption measurement showed that the aggregate has J-type characteristics and resonance Raman spectra gave the intrinsic explanation of molecular interaction in aggregate. Upon excitation at the optical allowed S2 state of aggregate, direct generation of triplet state via singlet fission(SF) mechanism was observed. Excitation dynamics was elucidated by fs-transient absorption spectroscopy and ns-flash photolysis, respectively. The triplet state life time of aggregate was found to be independent of the ambient oxygen molecules.

Near-Infrared S2 Fluorescence from Deprotonated Möbius Aromatic [32]Heptaphyrin.

This study revealed S2 fluorescence from deprotonated meso-pentafluorophenyl-substituted Möbius aromatic [32]heptaphyrin(1.1.1.1.1.1.1) that was formed upon treatment of neutral antiaromatic [32]heptephyrin with tetrabutylammonium fluoride. Higher excited-state dynamics and emission were studied by fs-transient absorption spectroscopy and a broad-band fluorescence upconversion technique. This is the first S2 fluorescence from chromophores with twisted Möbius topology, and the observation of S2 fluorescence in the near-infrared region has been unprecedented. The higher excited-state dynamics of neutral and deprotonated [32]heptaphyrins were compared by ultrafast transient absorption spectroscopy to understand the S2 fluorescence origin. In the antiaromatic [32]heptaphyrin, a fast time component of 65 fs was assigned as an internal conversion process from the SB state to the SQ state, which occurs prior to relaxation to the optically dark, lowest electronic state (SD). Therefore, the SQ state of the antiaromatic [32]heptaphyrin acts as a trap state intervening radiative transitions from the SB state to the S0 state. In deprotonated [32]heptaphyrin, the internal conversion from the SB state to the SQ state proceeds with a slower time constant of 150 fsfor owing to its rigid structure, helping the observation of its S2 fluorescence.

4-Nitrophenyl- and 4'-nitro-1,1'-biphenyl-4-carboxylates attached to Mo2 quadruple bonds: ground versus excited state M2δ-ligand conjugation.

From the reactions between Mo2(T(i)PB)4, where T(i)PB = 2,4,6-triisopropylbenzoate and two equivalents of the carboxylic acid LH (LH = 4-nitrobenzoic acid and 4'-nitro[1,1'-biphenyl]-4-carboxylic acid) the compounds trans-M2(T(i)PB)2L2 have been prepared: I (L = 4-nitrobenzoate and M = Mo), II (L = 4'-nitro-1,1'-biphenylcarboxylate and M = Mo) and III (L = 4-nitrobenzoate and M2 = MoW). The compounds have been characterized by (1)H NMR, UV-Vis and steady state emission spectroscopy, ns and fs transient absorption spectroscopy and cyclic voltammetry. These data are compared with predictions based on electronic structure calculations on model compounds where T(i)PB is substituted for formate. Together these data indicate stronger ground-state coupling of the Mo2δ and ligand π* systems in I relative to II but this order is reversed in the photo excited S1(1)MLCT state. Attempts to prepare the W2 containing analogs were unsuccessful.

Long-Lived Singlet and Triplet Charge Separated States in Small Cyclophane-Bridged Triarylamine–Naphthalene Diimide Dyads

Two different dyads containing a triarylamine (TAA) donor and a naphthalene-1,8:4,5-bis(dicarboximide) (NDI) acceptor bridged by either a [2.2]- or a [3.3]paracyclophane (CP) were synthesized. These dyads show a high population of long-lived charge separated (CS) singlet and triplet states. The lifetimes of these different spin states vary only by 1 order of magnitude. This unique situation is a consequence of both a large electronic coupling V and a large exchange coupling 2J. The population of the different CS spin states and therefore the charge recombination (CR) and intersystem crossing (ISC) kinetics were monitored by standard ns-transient absorption spectroscopy. Together with fs-transient absorption spectroscopy supported by electrochemistry, steady state fluorescence and steady state absorption spectroscopy a detailed model of the photoinduced processes was derived.