Ultrafast dynamics in multibranched structures with enhanced two-photon absorption

The understanding of the mechanism of the enhanced two-photon absorption (TPA) in multibranched chromophore systems is of importance to the design of materials with the large TPA cross-sections and for future applications. In this communication, the mechanism of enhanced TPA properties is investigated. For a dendritic model system, the excited-state dynamics for both population (T1-process) and phase relaxation (T2-process) processes involved are investigated by a combination of time-resolved spectroscopic techniques. The results of time-resolved fluorescence anisotropy are compared with previous results obtained from other branched chromophore systems. It is found that the PRL-701 trimer system, which possesses the large enhancement of two-photon absorption cross-section, gives a faster anisotropy decay (fluorescence upconversion and transient absorption), a longer population relaxation time (fluorescence lifetime), and a weaker coupling to the solvent (a larger photon echo peak shift initial value). New strategies for rational design of large TPA materials can be achieved based on a better understanding of the mechanism of the enhancement.     

Synthesis, two-photon absorption and AIE properties of multibranched thiophene-based triphenylamine derivatives with triazine core

Two new multibranched thiophene-based triarylamine derivatives with 1,3,5-triazine core are synthesized and characterized. Their one-and two-photon absorption properties and aggregation-induced emission effect have been investigated. Both the STAPA-based compounds are AIE active. The two-photon absorption (2PA) cross sections measured by the open aperture Z-scan technique are determined to be 620 and 1610 GM for STAPA-a and STAPA-b in chloroform,respectively, which dramatically increase with the introduction of alkyl chains. The relationship between their structures and properties on one-and two-photon absorption and aggregation-induced emission is discussed, which allows us to examine the effect of introducing alkyl chains. In addition, solvent effects also show a significant influence on the 2PA cross section. The two compounds with excellent AIE and 2PA properties provide attractive alternatives for the biophotonic materials.     

Enhanced two-photon absorption of novel four-branched chromophore via vibronic coupling

A novel four-branched chromophore TOZ-4 with starburst linker was synthesized and showed two-photon absorption cross-section (δ) as large as 5254 GM, which was principally resulted from vibronic coupling enhancement.     

Solvent effects on two-photon absorption of dialkylamino substituted distyrylbenzene chromophore

Solvent effects on the two-photon absorption of a symmetrical diamino substituted distyrylbenzene chromophore have been studied using the density functional response theory in combination with the polarizable continuum model. It is shown that the dielectric medium has a rather small effect both on the bond length alternation and on the one-photon absorption spectrum, but it affects significantly the two-photon absorption cross section. It is found that both one- and two-photon absorptions are extremely sensitive to the planarity of the molecule, and the absorption intensity can be dramatically reduced by the conformation distortion. It has led to the conclusion that the experimentally observed anomalous solvent effect on the two-photon absorption of dialkylamino substituted distyrylbenzene chromophores cannot be attributed to the intrinsic properties of a single molecule and its interaction with solvents.     

Fusing three perylenebisimide branches and a truxene core into a star-shaped chromophore with strong two-photon excited fluorescence and high photostability

A novel star-shaped chromophore, Tr-PBI, was constructed by fusing three perylenebisimide branches and a truxene core. Tr-PBI exhibits high photostability and excellent two-photon properties: the maximum of δ(TPA) is 11,000 GM at 990 nm and fluorescence quantum efficiency Φ is 0.40 in THF.     

Enhanced two-photon absorption with novel octupolar propeller-shaped fluorophores derived from triphenylamine

[structure: see text] Novel octupolar fluorophores derived from the symmetrical functionalization of a triphenylamine core with strong acceptor peripheral groups via phenylene-ethynylene linkers have been synthesized and shown to exhibit high fluorescence quantum yields, very large TPA cross-sections in the red-NIR region, and suitable photostability.     

Resolving the ultrafast dynamics of the anionic green fluorescent protein chromophore in water

The chromophore of the green fluorescent protein (GFP) is critical for probing environmental influences on fluorescent protein behavior. Using the aqueous system as a bridge between the unconfined vacuum system and a constricting protein scaffold, we investigate the steric and electronic effects of the environment on the photodynamical behavior of the chromophore. Specifically, we apply ab initio multiple spawning to simulate five picoseconds of nonadiabatic dynamics after photoexcitation, resolving the excited-state pathways responsible for internal conversion in the aqueous chromophore. We identify an ultrafast pathway that proceeds through a short-lived (sub-picosecond) imidazolinone-twisted (I-twisted) species and a slower (several picoseconds) channel that proceeds through a long-lived phenolate-twisted (P-twisted) intermediate. The molecule navigates the non-equilibrium energy landscape via an aborted hula-twist-like motion toward the one-bond-flip dominated conical intersection seams, as opposed to following the pure one-bond-flip paths proposed by the excited-state equilibrium picture. We interpret our simulations in the context of time-resolved fluorescence experiments, which use short- and long-time components to describe the fluorescence decay of the aqueous GFP chromophore. Our results suggest that the longer time component is caused by an energetically uphill approach to the P-twisted intersection seam rather than an excited-state barrier to reach the twisted intramolecular charge-transfer species. Irrespective of the location of the nonadiabatic population events, the twisted intersection seams are inefficient at facilitating isomerization in aqueous solution. The disordered and homogeneous nature of the aqueous solvent environment facilitates non-selective stabilization with respect to I- and P-twisted species, offering an important foundation for understanding the consequences of selective stabilization in heterogeneous and rigid protein environments.

Simulations on the aqueous green fluorescent protein (GFP) chromophore (in the equilibrium and non-equilibrium regimes) reveal that observed biexponential fluorescence originates from two competing torsional deactivation pathways.     

Two-photon absorption strength: a new tool for the quantification of two-photon absorption

In this paper, we define the two-photon absorption strength, a new characterization tool, similar to the oscillator strength, but for two-photon absorption. It allows the quantification of the two-photon absorption properties of molecular systems which are one-photon transparent. Its definition is such that the corresponding numerical values are around 100 for small molecules. We also show that this new theoretical tool allows the direct comparison of experimental and theoretical data without requiring the introduction of any arbitrary band width. As an example, the experimental and theoretical (AM1+CNDOS and HF+CIS3-21G) two-photon absorption properties of the 2,2'-bi(9,9-dihexylfluorene) molecule are compared.     

Conjugated chromophore near the quantum-confined cadmium sulfide cluster: quenched photoluminescence and enhanced two-photon absorption

Quenching effect of the photoluminescence of 1,2,4,5-tetrakis(4-pyridylvinyl)benzene in the presence of CdS colloids stabilized by inverse micelles was observed. The observed regularities of luminescence quenching by the quenchers of different size were studied. An increase in the two-photon absorption cross section (6.5 times higher) and in the two-photon-induced fluorescence intensity was observed for the composite solution when pumped by 740-nm laser irradiation. The results are in accord with theoretical prediction of enhancement of third-order optical nonlinearity of quantum-confined semiconductor.     

Aromatic core modified decaphyrins with the largest two-photon absorption cross-sections: syntheses and characterization

[structure: see text] Core-modified aromatic decaphyrins with 42pi conjugated electrons exhibit the highest two-photon absorption cross-section value (sigma(2) = 108,000 GM) known for any organic molecule, suggesting possible device applications in the field of nonlinear optics.     

Synthesis and two-photon properties of a multipolar chromophore containing indenofluorenyl units

A new multipolar fluorophore derived from triphenylamine as the core with diphenylaminoindenofluorenyl moieties incorporated at the peripheral positions has been synthesized and experimentally shown to possess strong two-photon absorptivities in near-IR region and intense upconverted visible emission under the irradiation of femtosecond laser pulses.     

Synthesis and two-photon properties of a multi-polar chromophore based on tetra-quinoxalinylethylene scaffold

A new multi-branched fluorophore derived from tetra-quinoxalinylethylene as the core with diphenylaminofluorene units incorporated at the peripheral positions has been synthesized via Pd-catalyzed Suzuki coupling and experimentally shown to possess strong solvent effect on its fluorescence emission and lifetime behaviors. The initial characterization also found that this dye molecule exhibits two-photon activities and effective optical power limiting properties in the near-IR region under the irradiation of nanosecond laser pulses.     

Quantum-classical modeling of nonlinear pulse propagation in a dissolved two-photon active chromophore

In the present work we outline the implications of a quantum-classical approach for modeling two-photon absorption of organic chromophores in solution. The approach joins many-photon absorption dynamic simulations with quantum chemical first principles calculations of corresponding excitation energies and transition matrix elements. Among a number of conclusions of the study, we highlight three: (i) The use of either short- or long-pulse excitation is demonstrated to switch the absorptive capacity of the nonlinear medium owing to enhancement of the nonlinear stepwise processes; (ii) The two-photon cross section strongly depends on the way in which the dephasing rate decays when the laser frequency is tuned off-resonant with the corresponding molecular transition; (iii) The results of the pulse propagation simulations based on electronic structure data obtained with a new Coulomb attenuated functional is shown to be in much better agreement with the experimental results than those based on data received with traditional density functionals.     

Study of the absorption and emission spectroscopy of "A-B" type photosensitive compounds including two-photon chromophore and benzophenone moiety

"A-B" type photosensitive compounds including two-photon chromophore and benzophenone moiety have been designed, synthesized and characterized. The UV-vis absorption and fluorescence emission of the compounds have been extensively studied in various solvents. The results show that the absorption of "A-B" type compounds displays obvious double absorption bands, one of which at short-wavelength is related to the benzophenone moiety, the other at long-wavelength is mainly contributed by chromophore. The emission of "A-B" type compounds at 500-700nm shows an "unexpected" blue-shift comparing with that of the sole chromophore. The photosensitive compounds with amino group display strong emission in apolar solvents and have a low fluorescence quantum yields in polar solvents. In contrast, the compounds without amino group exhibit strong fluorescence emission in polar solvents, and low fluorescence quantum yields in apolar solvents. The fluorescence quantum yields of "A-B" type compounds are higher than those of the sole chromophore. The discoveries suggest that charge redistribution induced by the introduction of benzophenone moiety plays a key role on the absorption and emission spectroscopy.     

Excited-state absorption and ultrafast relaxation dynamics of porphyrin, diprotonated porphyrin, and tetraoxaporphyrin dication

The relaxation dynamics of unsubstituted porphyrin (H2P), diprotonated porphyrin (H4P2+), and tetraoxaporphyrin dication (TOxP2+) has been investigated in the femtosecond-nanosecond time domain upon photoexcitation in the Soret band with pulses of femtosecond duration. By probing with spectrally broad femtosecond pulses, we have observed transient absorption spectra at delay times up to 1.5 ns. The kinetic profiles corresponding with the band maxima due to excited-state absorption have been determined for the three species. Four components of the relaxation process are distinguished for H2P: the unresolvably short B --> Qy internal conversion is followed by the Qy --> Qx process, vibrational relaxation, and thermalization in the Qx state with time constant approximately 150 fs, 1.8 ps, and 24.9 ps, respectively. Going from H2P to TOxP2+, two processes are resolved, i.e., B --> Q internal conversion and thermal equilibration in the Q state. The B --> Q time constant has been determined to be 25 ps. The large difference with respect to the B --> Qy time constant of H2P has been related to the increased energy gap between the coupled states, 9370 cm-1 in TOxP2+ vs 6100 cm-1 in H2P. The relaxation dynamics of H4P2+ has a first ultrafast component of approximately 300 fs assigned as internal conversion between the B (or Soret) state and charge-transfer (CT) states of the H4P2+ complex with two trifluoroacetate counterions. This process is followed by internal CT --> Q conversion (time constant 9 ps) and thermalization in the Q state (time constant 22 ps).     

Unveiling ultrafast dynamics in bridged bimetallic complexes using optical and X-ray transient absorption spectroscopies

In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers. Here, we use ultrafast optical and X-ray spectroscopies to elucidate the effects of metal–metal interactions in a bimetallic tetrapyridophenazine-bridged Os(ii)/Cu(i) complex. Despite having an appropriate driving force for Os-to-Cu hole transfer in the Os(ii) moiety excited state, no such charge transfer was observed. However, excited-state coupling between the metal centers is present, evidenced by variations in the Os MLCT lifetime depending on the identity of the opposite metal center. This coupling results in concerted coherent vibrations appearing in the relaxation kinetics of the MLCT states for both Cu and Os centers. These vibrations are dominated by metal–ligand contraction at the Cu/Os centers, which are in-phase and linked through the conjugated bridging ligand. This study shows how vibronic coupling between transition metal centers affects the ultrafast dynamics in bridged, multi-metallic systems from the earliest times after photoexcitation to excited-state decay, presenting avenues for tuning charge-transfer states through judicious choice of metal/ligand groups.

In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers.     

Nonperturbative modeling of two-photon absorption in a three-state system

The physics of the two-photon absorption process is investigated for a three-state system. The density-matrix equations for the two-photon interaction are solved in the steady-state limit assuming that the pump laser radiation is monochromatic. Collisional broadening, saturation, and Stark shifting of the two-photon resonance are investigated in detail by numerical solution of the steady-state density-matrix equations. Analytical expressions for the saturation intensity and the Stark shift are derived for the case where the single-photon transitions between the intermediate state and the initial and final states are far from resonance with the pump laser. For this case, it is found that the direction of the Stark shift is dependent on the relative magnitudes of the dipole-moment matrix elements for the single-photon transitions that couple the intermediate state with the initial and final states. Saturation and Stark shifting are also investigated for the case where the single-photon transitions between the intermediate state and the initial and final states are close to resonance with the pump laser.     

Confined ultrafast torsional dynamics of Thioflavin-T in a nanocavity

The influence of confinement in the supramolecular β-cyclodextrin nanocavity on the excited state torsional dynamics of the amyloid fibril sensor, Thioflavin-T, is explored using subpicosecond fluorescence up-conversion spectroscopy. In the presence of β-cyclodextrin, the emission intensity and the fluorescence lifetime of Thioflavin-T significantly increases, indicating the confinement effect of the nanocage on the photophysical behaviour of the dye. Detailed time-resolved fluorescence studies show an appreciable dynamic Stokes' shift for the dye in the β-cyclodextrin nanocavity. Analysis of the time-resolved area normalized emission spectra (TRANES) indicates the formation of an emissive TICT state. The rate of formation of the TICT state, as calculated from the time dependent changes in the peak frequency and the width of the emission spectra, is found to be substantially slower in the β-cyclodextrin nanocavity compared to that in bulk water. Present results indicate that ultrafast torsional motion in Thioflavin-T is significantly retarded due to confinement by the β-cyclodextrin nanocavity.