Two-photon absorption spectra (2PA) of a series of conjugated dimers and the corresponding monomer were studied in the near-IR region. All of the dimers show very large peak cross section values, sigma(2) = (3-10) x 10(3) GM (1 GM = 1 x 10(-50) cm(4) s photon(-1)), which is several hundred times larger than that obtained for the corresponding monomer in the same region. We explain such dramatic cooperative enhancement by a combination of several factors, such as strong enhancement of the lowest one-photon Q-transition, better resonance conditions in the three-level system, dramatic enhancement of the excited-state singlet-singlet transition, and parallel arrangement of consecutive transitions in dimers, as compared to perpendicular arrangement in the monomer. We show that the absolute values of the 2PA cross section in these molecules are quantitatively described by a quantum-mechanical expression, derived for the three-level model. We also demonstrate the possibility of singlet oxygen generation upon one- and two-photon excitation of these dimers, which makes them particularly attractive for photodynamic therapy.
We present the two-photon absorption (2PA) spectra of a series of conjugated porphyrin dimers and show that they possess extremely large intrinsic (femtosecond) peak 2PA cross sections, up to sigma2 = 1 x 104 GM in the near-IR region; these are among the highest values measured for any organic molecule. Moreover, we demonstrate that the second-order perturbation theory applied to a simple three-level model gives a perfect quantitative description of the observed 2PA cross section. By comparing all the factors of the three-level model for dimers with those of corresponding monomer (for which sigma2 = 20 GM), we explain an approximately 500-fold cooperative enhancement in sigma2 and find that the most important factor is the strength of excited-state transition. The matrix element of dipole moment of this transition amounts gigantic values of 30-40 D for conjugated porphyrin dimers, which can be accounted for a large delocalization radius (large electron-hole separation) in this state. We also demonstrate efficient generation of singlet oxygen upon one- and two-photon excitation of these porphyrin dimers, which can be useful for two-photon initiated photodynamic therapy of cancer.
We present the two-photon absorption (2PA) spectra of a series of conjugated porphyrin oligomers containing N = 2, 4, 8, and ca. 13 monomer units, meso-meso connected with butadiyne linkers. We demonstrate that, in the coplanar double-strand arrays, self-assembled upon addition of 4,4'-bipyridyl, the conjugation length increases dramatically, leading to very strong cooperative enhancement of 2PA. We analyze the scaling of 2PA in both the double-strand and rotationally free single-strand arrays and show how the effective conjugation length in both cases is linked to the observed 2PA properties. By introducing a "conjugation signature" for the 2PA strength, we show that, in double-strand arrangement, the conjugation embraces the whole molecule up to the tetramer level, whereas in single-strand arrangement, it is always less than N, except for N = 2, but keeps increasing until N = 8. Our finding of extremely strong 2PA cross section, sigma2 approximately 105 GM, in double-strand oligomers peaking at 1.3 mum can find use for signal processing in fiber-optic devices.
We study two-photon absorption (2PA) in two series of new free-base porphyrins with 4-(diphenylamino)stilbene or 4,4'-bis-(diphenylamino)stilbene (BDPAS) attached via pi-conjugating linkers at the porphyrin meso-position. We show that this new substitution modality increases the 2PA cross section in the Soret band region (excitation wavelength 750-900 nm) of the core porphyrin by nearly 2 orders of magnitude, from sigma(2) approximately 10 GM for the meso-phenyl-substituted analogue to sigma(2) approximately 10(3) GM for the ethynyl-linked BDPAS-porphyrin dyad. The 2PA properties are quantitatively described by considering two different and interfering 2PA quantum transition pathways. The first path involves virtual transition via intermediate one-photon resonance. The second path bypasses the intermediate resonance and occurs due to a large permanent dipole moment difference between the ground and the final electronic states. To our best knowledge, this is the first experimental observation of the combined effect of these two pathways on one particular two-photon transition, resulting in quantum-interference-modulated 2PA strength.
Degenerate two-photon absorption (2PA) of a series of organic fluorophores is measured using femtosecond fluorescence excitation method in the wavelength range, λ2PA = 680-1050 nm, and ~100 MHz pulse repetition rate. The function of relative 2PA spectral shape is obtained with estimated accuracy 5%, and the absolute 2PA cross section is measured at selected wavelengths with the accuracy 8%. Significant improvement of the accuracy is achieved by means of rigorous evaluation of the quadratic dependence of the fluorescence signal on the incident photon flux in the whole wavelength range, by comparing results obtained from two independent experiments, as well as due to meticulous evaluation of critical experimental parameters, including the excitation spatial- and temporal pulse shape, laser power and sample geometry. Application of the reference standards in nonlinear transmittance measurements is discussed.
The linear and nonlinear optical properties of a series of linear and cross-conjugated platinum(II) acetylide complexes that contain extended p-(phenylene vinylene) chromophores are reported. The complexes exhibit very high femtosecond two-photon absorption (2PA) cross section values (σ(2) up to 10,000 GM), as measured by nonlinear transmission (NLT) and two-photon excited fluorescence (2PEF) methods. The large 2PA cross sections span a broad range of wavelengths, 570-810 nm, and they overlap with the triplet excited state absorption. Spectral coincidence of high cross section 2PA and triplet absorption is a key feature giving rise to efficient dual-mode optical power limiting (OPL).
We study instantaneous two-photon absorption (2PA) in a series of nominally quasi-centrosymmetric trans-bis(tributylphosphine)-bis-(4-((9,9-diethyl-7-ethynyl-9H-fluoren-2-yl) ethynyl)-R)-platinum complexes, where 11 different substituents, R = N(phenyl)(NPh), NH, OCH, t-butyl, CH, H, F, CF, CN, benzothiazole, and NO, represent a range of electron-donating (ED) and electron-withdrawing (EW) strengths, while the Pt core acts as a weak ED group. We measure the 2PA cross section in the 540-810 nm excitation wavelength range by complementary femtosecond two-photon excited fluorescence (2PEF) and nonlinear transmission (NLT) methods and compare the obtained values to those of the Pt-core chromophore and the corresponding noncentrosymmetric side group (ligand) chromophores. Peak 2PA cross sections of neutral and ED-substituted Pt complexes occur at S → S transitions to higher energy states, above the lowest-energy S → S transition, and the corresponding values increase systematically with increasing ED strength, reaching maximum value, σ ∼ 300 GM (1 GM = 10 cm s), for R = NPh. At transition energies overlapping with the lowest-energy S → S transition in the one-photon absorption (1PA) spectrum, the same neutral and ED-substituted Pt complexes show weak 2PA, σ < 30-100 GM, which is in agreement with the nearly quadrupolar structure of these systems. Surprisingly, EW-substituted Pt complexes display a very different behavior, where the peak 2PA of the S → S transition gradually increases with increasing EW strength, reaching values σ = 700 GM for R = NO, while in the S → S transition region the peak 2PEF cross section decreases. We explained this effect by breaking of inversion symmetry due to conformational distortions associated with low energy barrier for ground-state rotation of the ligands. Our findings are corroborated by theoretical calculations that show large increase of the permanent electric dipole moment change in the S → S transition when ligands with strong EW substituents are twisted by 90° relative to the planar chromophore. Our NLT results in the S → S transition region are quantitatively similar to those obtained from the 2PEF measurement. However, at higher transition energy corresponding to S → S transition region, the NLT method yields effective multiphoton absorption stronger than the 2PEF measurement in the same systems. Such enhancement is observed in all Pt complexes as well as in all ligand chromophores studied, and we tentatively attribute this effect to nearly saturated excited-state absorption (ESA), which may occur if 2PA from the ground state is immediately followed by strongly allowed 1PA to higher excited states.
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