Through click chemistry, triazole and triazolium groups have been explored to recognize anions through C-H···A(-) hydrogen-bonding complexion. Herein, we demonstrate evidence of fluoride-induced deprotonation of a C-H bond and its application in fluoride detection. The combination of fluorene and triazolium units produced a highly selective fluorescence turn-on prototype sensor for fluoride. The interactions between the C-H bond and F(-) were studied by fluorescence spectroscopy and (1)H NMR titrations. Test papers were prepared to detect fluoride in aqueous media at concentrations down to 1.9 ppm, important for estimating whether the fluoride concentration in drinking water is at a safe level.

A new series of unsymmetrical diphenylaminofluorene-based chromophores with various strong π-electron acceptors were synthesized and fully characterized. The systematic alteration of the structural design facilitated the investigation of effects such as molecular symmetry and strength of electron-donating and/or withdrawing termini have on optical nonlinearity. In order to determine the electronic and geometrical properties of the novel compounds, a thorough investigation was carried out by a combination of linear and nonlinear spectroscopic techniques, single crystal X-ray diffraction, and quantum chemical calculations. Finally, on the basis of two-photon absorption (2PA) cross sections, the general trend for π -electron accepting ability, i.e., ability to accept charge transfer from diphenylamine was: 2-pyran-4-ylidene malononitrile (pyranone) > dicyanovinyl > bis(dicyanomethylidene)indane > 1-(thiophen-2-yl)propenone > dicyanoethylenyl > 3-(thiophen-2-yl)propenone. An analog with the 2-pyran-4-ylidene malononitrile acceptor group exhibited a nearly three-fold enhancement of the 2PA< δ (1650 GM at 840 nm), relative to other members of the series.

The ability to rapidly detect biologically and environmentally significant metal ions such as zinc and mercury is important to study a number of important cellular and environmental processes. Hydrophilic bis(1,2,3-triazolyl)fluorene-based derivatives, containing a 1,2,3-triazole-based recognition moiety, were synthesized through Click chemistry and characterized by UV-vis absorption, fluorescence emission, and two-photon absorption as new fluorescence sensing probes, selective for Zn 2+ and Hg 2+ ions. The UV-vis absorption and fluorescence emission spectra of the complexes exhibited blue-shifted absorption and emission spectra upon chelation to Zn 2+ and Hg 2+ ions, resulting in ca. two-fold enhancement in fluorescence. Fluorometric titration revealed that 1:2 and 1:3 ligand to metal complexes formed with binding constants of 10 8 and 10 16 for Zn 2+ and Hg 2+ , respectively. The two-photon absorption cross sections for the probes and probe-metal ion complexes ranged from 200-350 GM at 800 nm. These novel fluorescent compounds may have potential as new metal ion sensors to probe cellular and biological environments.

Comprehensive linear photophysical and photochemical characterization, two-photon absorption (2PA) properties, and femtosecond excited-state dynamics of a symmetrical fluorene derivative 2-(2,6-bis((E)-2-(7-(diphenylamino)-9,9-dihexyl-9H-fluoren-7-yl)vinyl)-4H-thiopyran-4-ylidene)malononitrile (1) are reported. The linear one-photon absorption (1PA), steady-state fluorescence, excitation, and excitation anisotropy spectra of 1 were investigated in organic solvents of different polarities at room temperature, exhibiting rather complex absorption and emission behavior. The relatively strong 2PA of thiopyranyl 1 was investigated by the open aperture femtosecond Z-scan technique in the main long wavelength 1PA contour with maxima cross sections up to 600−700 GM. Femtosecond dynamics of the excited-state absorption (ESA) and gain processes in 1 exhibited fast complicated relaxation phenomena with a strong dependence on solvent polarity and a weak dependence on excitation wavelength. The nature of the observed transient absorption kinetics was explained based on the short-lived ESA bands of 1 and solvate relaxation phenomena. Quantum chemical calculations, based on density functional theory, were employed for additional analysis of the 1PA and 2PA properties of 1.

The photophysical, photochemical, two-photon absorption (2PA), and metal ion sensing properties of a new fluorene derivative (E)-1-(7-(4-(benzo[d]thiazol-2-yl)styryl)-9,9-bis(2-(2-ethoxyethoxy)ethyl)-9H-fluoren-2-yl)-3-(2-(9,10,16,17,18,19,21,22,23,24-decahydro-6H dibenzo[h,s][1,4,7,11,14,17]trioxatriazacycloicosin-20(7H)-yl)ethyl)thiourea (1) were investigated in organic and aqueous media. High sensitivity and selectivity of 1 to Zn2+ in THF and a water/ACN mixture were shown by both absorption and fluorescence titration. The observed complexation processes corresponded to 1:1 stoichiometry with the range of binding constants ~ (2–3)·105 M−1. The degenerate 2PA spectra of 1 and 1:Zn2+ complex were obtained in the 640–900 nm spectral range, with the maximum values of two-photon action cross section for ligand:metal complex ~ (90–130) GM, using a standard two-photon induced fluorescence methodology under femtosecond excitation. The nature of the 2PA bands was analyzed by quantum chemical methods and a specific dependence on metal ion binding processes was shown. Ratiometric fluorescence detection (420/650 nm) provided a good dynamic range (10−4 to 10−6 M) for detecting Zn2+, which, along with the good photostability and 2PA properties of probe 1. makes it a good candidate in two-photon fluorescence microscopy imaging and sensing of Zn ions.