Synthesis, photophysical, and two-photon absorption properties of elongated phosphane oxide and sulfide derivatives.

A series of rod-shaped and related three-branched push-pull derivatives containing phosphane oxide or phosphane sulfide (PO or PS)-as an electron-withdrawing group conjugated to electron-donating groups, such as amino or ether groups, with a conjugated rod consisting of arylene-vinylene or arylene-ethynylene building blocks-were prepared. These compounds were efficiently synthesized by a Grignard reaction followed by Sonogashira coupling. Their photophysical properties including absorption, emission, time-resolved fluorescence, and two-photon absorption (TPA) were investigated with special attention to structure-property relationships. These fluorophores show high fluorescence quantum yields and solvent-dependent experiments reveal that efficient intramolecular charge transfer occurs upon excitation, thereby leading to highly polar excited states, the polarity of which can be significantly enhanced by playing on the end groups and conjugated linker. Rod-shaped and related three-branched systems show similar fluorescence properties in agreement with excitation localization on one of the push-pull branches. By using stronger electron donors or replacing the arylene-ethynylene linkers with an arylene-vinylene one induces significant redshifts of both the low-energy one-photon absorption and TPA bands. Interestingly, a major enhancement in TPA responses is observed, whereas OPA intensities are only weakly affected. Similarly, phosphane oxide derivatives show similar OPA responses than the corresponding sulfides but their TPA responses are significantly larger. Finally, the electronic coupling between dipolar branches promoted by common PO or PS acceptor moieties induces either slight enhancement of the TPA responses or broadening of the TPA band in the near infrared (NIR) region. Such behavior markedly contrasts with triphenylamine-core-mediated coupling, which gives evidence for the different types of interactions between branches.

The effectiveness of essential-state models in the description of optical properties of branched push-pull chromophores.

In this paper we present the synthesis, spectroscopic characterization and theoretical modelling of two pairs of correlated dipolar and octupolar donor-acceptor conjugated chromophores, based on the triphenylamine branching centre. The two pairs of chromophores differ for the electron withdrawing end-groups. Linear absorption, fluorescence and two-photon absorption of all the compounds in different solvents can be well described by the use of charge-resonance theoretical models based on essential-state descriptions of the electronic structure, and taking into account the coupling to effective molecular vibrations and to polar solvation degrees of freedom. On the contrary, the alternative Frenkel exciton model does not provide a good description of the observed behavior. The robustness of the proposed theoretical models is demonstrated for the first time by the fact that the modulation of a single molecular parameter (the one linked to the electron-withdrawing ability of the end groups) is enough to describe the evolution of the spectroscopic properties along the whole series of chromophores, both "intra-pair" and "inter-pair". The effectiveness of the approach suggests that this kind of theoretical modelling can be very useful to predict different properties of the compounds at hand or of correlated structures of increasing complexity, such as dendrons and dendrimers, giving a guide to the synthesis of (macro)molecules for applications in light-emitting and nonlinear optical devices, artificial light-harvesting systems or optical imaging of living tissues.

Molecular interaction between apo or holo alpha-lactalbumin and lysozyme: formation of heterodimers as assessed by fluorescence measurements.

In a previous work, we reported that contrary to native calcium-loaded alpha-lactalbumin (holo alpha-LA), calcium-depleted form (apo alpha-LA) has the ability to self-assemble with lysozyme (LYS) to form different supramolecular structures in temperature-dependent manner. In this study, we examine what happens at molecular scale using fluorescence techniques. Fluorescence anisotropy coupled with fluorescence lifetime measurements provides a means to measure intermolecular interactions. We showed that LYS interacts with both apo alpha-LA and holo alpha-LA to form oligomers, assumed to be heterodimers, at 10 degrees C and 45 degrees C. The dissociation constants for dimerization were found to be in the muM range and increased significantly with increasing ionic strength from 39 to 124 mM. Although the binding constants of holo alpha-LA-LYS and apo alpha-LA-LYS complexes were of the same order of magnitude, the shape or conformation of formed heterodimers differed as assessed by fluorescence parameters in particular correlation time calculations. Such conformation differences could explain why holo alpha-LA-LYS complexes are trapped as heterodimers while the apo alpha-LA-LYS complexes have the ability to further self-assemble into various supramolecular structures.