Two-photon polarity probes built from octupolar fluorophores: synthesis, structure-properties relationships, and use in cellular imaging.

A series of octupolar fluorophores built from a triphenylamine (TPA) core connected to electron-withdrawing (EW) peripheral groups through conjugated spacers has been synthesized. Their photoluminescence, solvatochromism, and two-photon absorption (2PA) properties were systematically investigated to derive structure-property relationships. All derivatives exhibit two 2PA bands in the 700-1000 nm region: a first band at low energy correlated with a core-to-periphery intramolecular charge transfer that leads to an intense 1PA in the blue-visible range, and a second more intense band at higher energy due to an efficient coupling of the branches through the TPA core. Increasing the strength of the EW end groups or the length of the conjugated spacers and replacing triple-bond linkers with double bonds induces both enhancement and broadening of the 2PA responses, thereby leading to cross-sections up to 2100 GM at peak and higher than 1000 GM over the whole 700-900 nm range. All derivatives exhibit intense photoluminescence (PL) in low- to medium-polarity environments (with quantum yields in the 0.5-0.9 range) and display a strong positive solvatochromic behavior (with Lippert-Mataga specific shifts ranging from 15,000 to 27,500 cm(-1)), triple bonds, and phenyl moieties in the conjugated spacers, thereby leading to larger sensitivities than those of double bonds and thienyl moieties. More hydrophilic derivatives were also shown to be biocompatible, to retain their 2PA and PL properties in biological conditions, and finally to be suitable as polarity sensors for multiphoton cell imaging.

Octupolar derivatives functionalized with superacceptor peripheral groups: synthesis and evaluation of the electron-withdrawing ability of potent unusual groups.

Novel tripodal derivatives with a triphenylamine core and that bear "superacidifiers" (i.e., fluorinated sulfoximinyl blocks) or novel sulfiliminyl moieties as peripheral groups were synthesized. These new chromophores show strong absorption in the near-UV region and emission in the visible region. The fluorinated sulfoximinyl moieties were found to behave as potent auxochromic and electron-withdrawing (EW) groups, thus leading to redshifted absorption and emission. These moieties promote a core-to-periphery intramolecular charge transfer (ctp-ICT) transition, the energy of which was found to be correlated to their EW strength. In this study, we provide evidence of a linear correlation between the Hammett constant (σ(p)) values and the electronic gap between the ground and first excited state of the three-branched derivatives. This in turn was used to derive σ(p) values of fluorinated sulfoximinyl moieties. These EWGs show unprecedentedly high σ(p) values, up to 1.45 relative to 0.8 for NO(2). Also, by using this method, the sulfiliminyl moiety was shown to exhibit similar EW strength as NO(2) , while promoting improved transparency and solubility. Finally, the superior EW strength of the fluorinated sulfoximine peripheral moieties was shown to induce significant enhancement of the two-photon absorption responses in the red near-IR region of the three-branched derivatives relative to similar octupoles that bear more usual strong EW groups. These characteristics (improved nonlinear responses or transparency) open new routes for the design of nonlinear optical (NLO) chromophores for optical limiting or electro-optical modulation. Such building blocks could also be of interest for optoelectronic applications, including the development of solar cells.

Fluorogenic click reaction.

Fluorogenic Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reactions have emerged as a powerful tool for bioconjugation, materials science, organic synthesis and drug discovery. This review highlights the design of the recent development of fluorogenic CuAAC reactions as well as their applications.

Simultaneous control of emission localization and two-photon absorption efficiency in dissymmetrical chromophores.

The aim of the present work is to demonstrate that combined spatial tuning of fluorescence and two-photon absorption (TPA) properties of multipolar chromophores can be achieved by introduction of slight electronic chemical dissymmetry. In that perspective, two model series of structurally related chromophores have been designed and investigated. One is based on rod-like quadrupolar chromophores bearing either two identical or different electron-donating (D) end groups and the other on three-branched octupolar chromophores built from a trigonal donating moiety bearing identical or different acceptor (A) peripheral groups. The influence of the electronic dissymmetry is investigated by combined experimental and theoretical studies of the linear and nonlinear optical properties of dissymmetrical chromophores compared to their symmetrical counterparts. In both types of systems (i.e., quadrupoles and octupoles), experiments and theory reveal that excitation is essentially delocalized and that excitation involves synchronized charge redistribution (i.e., concerted intramolecular charge transfer) between the different D and A moieties within the multipolar structure. In contrast, the emission stems only from a particular dipolar subunit bearing the strongest D or A moiety due to fast excitation localization after excitation, prior to emission. Hence, control of emission characteristics (polarization and emission spectrum), can be achieved, in addition to localization, by controlled introduction of electronic dissymmetry (i.e., replacement of one of the D or A end-groups by a slightly stronger D' or A' unit). Interestingly, slight dissymmetrical functionalization of both quadrupolar and octupolar compounds does not lead to significant loss in TPA responses and can even be beneficial due to the spectral broadening and peak position tuning that it allows. This study thus reveals an original molecular engineering route allowing TPA enhancement in multipolar structures, due to concerted core-to-periphery or periphery-to-core intramolecular charge redistribution upon excitation, while providing for control of emission localization. Such a route could be extended to more intricate (dendritic) and multipolar (3D) systems.

A novel rearrangement of fluorescent human thymidylate synthase inhibitor analogues in ESI tandem mass spectrometry.

Cu(I) catalyzed alkyne-azide cycloaddition reaction was employed to synthesize a series of anthracene-based human thymidylate synthase (hTS) inhibitor analogues. The triazolo-anthracene derivatives were characterized by ESI-MS/MS and a novel rearrangement reaction in ESI-MS/MS was observed. The mechanism is proposed whereby the protonated triazolo-anthracene derivative forms a carbocation, and then the carbocation electrophilically attacks an anthracene moiety resulting in formation of a rearrangement ion. Moreover, the carbocation prefers to attack the gamma position rather than the alpha or beta position of the anthracene moiety by an electrophilic substitution mechanism.

The synthesis and one- and two-photon optical properties of dipolar, quadrupolar and octupolar donor-acceptor molecules containing dimesitylboryl groups.

Two series of related donor-acceptor conjugated dipolar, pseudo-quadrupolar (V-shaped) and octupolar molecular systems based on the p-dimesitylborylphenylethynylaniline core, namely, 4-(4-dimesitylborylphenylethynyl)-N,N-dimethylaniline, 4-[4-(4-dimesitylborylphenylethynyl)phenylethynyl]-N,N-dimethylaniline, 3,6-bis(4-dimesitylborylphenylethynyl)-N-n-butylcarbazole and tris[4-(4-dimesitylborylphenylethynyl)phenyl]amine, and on the E-p-dimesitylborylethenylaniline motif, namely, E-4-dimesitylborylethenyl-N,N-di(4-tolyl)aniline, 3,6-bis(E-dimesitylborylethenyl)-N-n-butylcarbazole and tris(E-4-dimesitylborylethenylphenyl)amine have been synthesised by palladium-catalyzed cross-coupling and hydroboration routes, respectively. Their absorption and emission maxima, fluorescence lifetimes and quantum yields have been obtained and their two-photon absorption (TPA) spectra and TPA cross-sections have been examined. Of these systems, the octupolar compound tris(E-4-dimesitylborylethenylphenyl)amine has been shown to exhibit the largest TPA cross-section among the two series of approximately 1000 GM at 740 nm. Its TPA performance is comparable to those of other triphenylamine-based octupoles of similar size. The combination of such large TPA cross-sections and high emission quantum yields, up to 0.94, make these systems attractive for applications involving two-photon excited fluorescence (TPEF).

Effect of branching on two-photon absorption in triphenylbenzene derivatives.

The photophysical and linear and nonlinear spectral properties of octupolar compounds with a triphenylbenzene core are investigated and compared with properties of corresponding dipolar branches. A correlation is found between the solvatochromic behavior and the two-photon absorption cross section. Moreover, the nature of the core is found to be responsible for the nature of the coupling between branches; in the studied case only (weak) electrostatic interactions are effective, while other cores, like the triphenylamine moiety, are able to promote coherent coupling between the branches, leading to strongly nonadditive properties.

Towards "smart" multiphoton fluorophores: strongly solvatochromic probes for two-photon sensing of micropolarity.

New fluorophores, combining broad, very high two-photon absorption in the near-infrared region with a marked dependence of their emission spectra on solvent polarity, have been designed as model probes for two-photon sensing of the chemical environment.