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The Ullmann amination reaction was utilized to provide access to a number of fluorene analogues from common intermediates, via facile functionalization at positions 2, 7, and 9 of the fluorene ring. Through variation of amine or iodofluorene derivative, analogues bearing substitutents with varying electron-donating and electron-withdrawing ability, e.g., diphenylamino, bis-(4-methoxyphenyl)amine, nitro, and benzothiazole, were synthesized in good yield. The novel fluorene derivatives were fully characterized, including absorption and emission spectra. Didecylation at the 9-position afforded remarkably soluble derivatives. Target compounds 4, 5, and 9 are potentially useful as fluorophores in two-photon fluorescence microscopy. Their UV-vis spectra display desirable absorption in the range of interest suitable for two-photon excitation by near-IR femtosecond lasers. Preliminary measurements of two-photon absorption indicate the derivatives exhibit high two-photon absorptivity, affirming their potential as two-photon fluorophores. For example, using a 1,210 nm femtosecond pump beam, diphenylaminobenzothiazolylfluorene 4 exhibited nondegenerate two-photon absorption, with two-photon absorptivity (delta) of ca. 820 x 10(-50) cm(4) s photon(-1) molecule(-1) at the femtosecond white light continuum probe wavelength of 615 nm.

The degenerate and nondegenerate two-photon absorption (2PA) spectra for a symmetric and an asymmetric fluorene derivative were experimentally measured in order to determine the effect of intermediate state resonance enhancement (ISRE) on the 2PA cross section delta. The ability to tune the individual photon energies in the nondegenerate 2PA (ND-2PA) process afforded a quantitative study of the ISRE without modifying the chemical structure of the investigated chromophores. Both molecules exhibited resonant enhancement of the nonlinearity with the asymmetric compound showing as much as a twentyfold increase in delta. Furthermore, the possibility of achieving over a one order of magnitude enhancement of the nonlinearity reveals the potential benefits of utilizing ND-2PA for certain applications. To model ISRE, we have used correlated quantum-chemical methods together with the perturbative sum-over-states (SOS) expression. We find strong qualitative and quantitative correlation between the experimental and theoretical results. Finally, using a simplified three-level model for the SOS expression, we provide intuitive insight into the process of ISRE for ND-2PA.

Efficient Pd-catalyzed Heck coupling methodology was employed to provide two new fluorene derivatives with phosphonate (2) and nitro (3) electron-withdrawing functionalities. Both derivatives exhibit two-photon absorption (2PA), as determined by nonlinear absorption measurements using a femtosecond pump/white light continuum probe “NLO spectrometer”. Both fluorene derivatives have high 2PA cross sections (650 and 1300 × 10-50 cm4 s photon-1 molecule-1 for compounds 2 and 3, respectively).

We report image formation via photoinduced fluorescence changes in a polymeric medium with nondestructive two-photon fluorescence readout of a multilayer structure. A two-photon absorbing fluorescent dye possessing functional groups with differential basicity, (7-benzothiazolyl-9,9-didecyl-2,2-(N,N-diphenylamino)fluorene) (1), underwent protonation in the presence of a photoinduced acid generator upon exposure to a broadband UV light source or femtosecond near-IR laser irradiation. Solution studies demonstrated formation of monoprotonated and diprotonated species upon irradiation, each resulting in distinctly different absorption and fluorescence properties. The fluorescence of the original, neutral fluorophore was reduced upon monoprotonation, leading to a concomitant increase in fluorescence at longer wavelengths due to the monoprotonated form. Experiments in polymer films demonstrate the changes in fluorescence properties of the fluorophores can be employed for a write-once read-many (WORM) data storage medium with a two-photon fluorescence readout. Two-channel, two-photon fluorescence imaging provided both “positive” and “negative” image readout capability.

High-order multiphoton excitation processes are becoming a reality for fluorescence imaging and phototherapy treatment because they afford minimization of scattered light losses and a reduction of unwanted linear absorption in the living organism transparency window, making them less susceptible to photodamage, while improving the irradiation penetration depth and spatial resolution. We report the four-photon-excited fluorescence emission of (7-benzothiazol-2-yl-9,-didecylfluoren-2-yl)diphenylamine in hexane and its four-photon absorption cross section sigma4' = 8.1 x 10(-109) cm8 s3 photon(-3) for the transition S0 --> S1 when excited at 1600 nm with a tunable optical parametric generator (OPG) pumped by picosecond laser pulses. When pumped at 1200 nm, three-photon absorption was observed, corresponding to the same transition.

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