Two-photon Absorption Cross-section Values Research Articles

Synthesis and two-photon absorption properties of multi-branched styryl derivatives containing π-bond and σ-electron pair as bridge based on 1,3,5-triazine

A series of new one, two, and three-branched two-photon absorption triazine derivatives with a π-bond and a σ-electron pair as a bridge have been synthesized and their photophysical properties have been systematically investigated. These chromophores showed obvious solvatochromic effects, i.e., significant bathochromic shifting of the emission spectra and larger Stokes shifts were observed in more polar solvents mainly due to intra-molecular charge transfer (ICT). The two-photon absorption (2PA) cross-section values were determined by the two-photon excited fluorescence (TPEF) measurements in DMF. This result further proved that a σ-electron pair as a bridge is an efficient way to transfer charge as well as a π bridge, and that their 2PA cross-section values (δ) increase with increasing branch number.

Planar tetra-coordinate carbon resulting in enhanced third-order nonlinear optical response of metal-terminated graphene nanoribbons

Metal-terminated graphene nanoribbons (M-GNRs) with planar tetra-coordinate carbons (PtC) are investigated theoretically for a third-order nonlinear optical (NLO) response by using the sum-over-states (SOS) method. The third order NLO polarizability, two-photon absorption (TPA) and nonlinear reflectivity are investigated within the third-harmonic generation (THG) or degenerate four-wave mixing (DFWM) processes. The origins of third order NLO polarizability and TPA are analyzed in terms of the charge transfer process, which indicates that tetra-coordinate carbons in M-GNRs have an important role in the third-order NLO response. The dynamic nonlinear reflectivity of the M-GNR presents a resonant characteristic due to the large third order NLO polarizability. Moreover, the third order NLO polarizability and TPA cross section values increase as the ribbon size increases in the low frequency region of incident light, which indicates that their NLO properties can be tailored by controlling the ribbon size. This paper aims to shed light on the design of NLO properties and understanding of the NLO response mechanisms of graphene related materials.

A new 2,2′:6′,2′′-terpyridine-based ligand and its complexes: structures, photophysical properties and DFT calculations to evaluate the halogen effect on the TPA

A novel 2,2':6',2′′-terpyridine-based ligand (L) and eight complexes have been synthesized and fully characterized. Six of these complexes ([CdLBr2]2·CHCl3 (2), ZnLI2 (3), [CdLI2]2·CH2Cl2 (4), ZnL(SCN)2·CHCl3 (5), [ZnL2]2(ClO4)4·7H2O (7) and [CdL2](ClO4)2·CH3OH (8)) were determined by single crystal X-ray diffraction analysis. Various weak interactions, including hydrogen bonds (C–H⋯N, C–H⋯X), C–H⋯π and π–π interactions played significant roles in the final supramolecular structures. Linear and nonlinear optical properties of the ligand and eight complexes are described. Experimental results reveal that two-photon absorption (TPA) cross-sections of these complexes are extraordinarily larger than that of the ligand, with maximum values of 97, 661, 787, 218, 133, 613, 230, 384 and 241 GM for L and complexes 1–8 in DMF, respectively. Density functional theory (DFT) calculations were performed on 1–6 and revealed that the halogen affects the accepting capability of surrounding metals due to different electron inductive effects, in the order Br > SCN > I. Thus, this in turn affects the TPA cross-section values. The results indicate that the TPA cross-sections vary in the order Br > SCN > I, which is consistent with the experimental results.

Synthesis of chromophores with porphyrin core and triphenylamine branching effect on the properties of linear/two-photon absorption

The synthesis of a serial new triphenylamine-multibranching chromophores with porphyrins “core” were reported and UV–vis absorption, one/two-photon fluorescence and two-photon absorption (TPA) cross-section were investigated. The triphenylamine-branching effect on their properties, including the different branches numbers and different generational multibranches were investigated in detail. The results show the different branches numbers and the different generational multibranches had a remarkable effect on the absorption and one/two-photon fluorescence properties of these chromophores. The two-photon absorption cross-section value ( σ s ) of the higher generational multibranched triphenylamine chromophore TPP-(G2X) 3 is 1058.25 GM, which is three times bigger than the others. Comparatively, the higher generational multibranched triphenylamine effect shows more significant contribution to two-photon absorption enhancement and obviously improves two-photon absorption cross-section behavior. This is greatly valuable for designing and synthesizing novel TPA materials.

Novel triphenylamine-cored two-photon absorbing dyes for labeling of biomolecules

Two novel, V-shaped and Y-shaped dipicolinate derivatives branched from triphenylamine, {4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl)vinyl]}- N-phenyl- N-{4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl)vinylphenyl]}aniline ( 1) and {4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl) vinyl]}- N, N-bis {4-[(E)-2-(2,6-dimethoxycarbonyl pyridin-4-yl)vinylphenyl]}aniline ( 2) were synthesized. These compounds were designed for large two-photon absorption and in particular for labeling of biomolecules. Their linear absorption, fluorescence properties and their two-photon absorption properties as well as two-photon fluorescence cell imaging were examined. When excited at 800 nm, the two-photon absorption cross-section values of chromophores 1 and 2 in THF were 208 GM, 376 GM, respectively. These two-photon absorbing dyes possess reasonable water solubility, strong chelating ability and display a large set of reactivity for coupling to biomolecules, which are apparently due to the two methoxycarbonyl groups in pyridine ring. This work suggests that chromophores 1 and 2 are promising labels potentially applicable for the tracking of biomolecules using two-photon scanning microscopy.

Comparative photophysics of sapphyrin derivatives: effects of confused and fused pyrrole rings

We have investigated the photophysical properties of [22] π-conjugated pentapyrrolic systems, sapphyrin, N-confused and N-fused sapphyrins, with a particular focus on the effects of confused and fused pyrrole rings on their electronic structures using steady-state and time-resolved spectroscopic methods, two-photon absorption cross-section (σ(2)) measurements and quantum mechanical calculations. The absorption spectra of N-confused and N-fused sapphyrins exhibit relatively red-shifted features compared to sapphyrin. In parallel with these spectral features, the reduced HOMO–LUMO gaps were observed in going from sapphyrin to N-fused sapphyrin. In the analysis of the anisotropy of the induced current density (AICD), N-confused and N-fused sapphyrins show that extra π-electrons in confused and fused pyrrole rings contribute to the extension of their π-conjugation pathways. Slightly larger twophoton absorption cross-section values of N-confused and N-fused sapphyrins (3250 and 3900 GM) than that of sapphyrin (2900 GM) also reflect an enhanced π-conjugation effect due to bicyclic and endocyclic extensions in π-conjugation pathways, respectively. The excited singlet and triplet state lifetimes of N-confused sapphyrin were determined to be 60 ps and 1 μs, respectively, due to conformational change and acceleration of nonradiative decay processes, being in a sharp contrast with those of sapphyrin (2.4 ns and 13 μs, respectively). In the case of N-fused sapphyrin, very short singlet excited-state lifetime of 5 ps was detected probably due to the excited-state NH-tautomerization process which enhances nonradiative decay processes.

Synthesis, Crystal Structures, Photophysical Properties, and Bioimaging of Living Cells of Bis-β-Diketonate Phenothiazine Ligands and Its Cyclic Dinuclear Complexes

Two bis-β-diketones, RCOCH(2)CO-EPTZ-COCH(2)COR (EPTZ = 10-ethylphenothiazine; R = C(6)H(5) for H(2)L(1) and CF(3) for H(2)L(2)) and their cyclic dinuclear Zn(II), Cd(II), Ni(II), Mn(II), Cu(II), Co(II) complexes have been synthesized and fully characterized. Their crystal structures were determined by single crystal X-ray diffraction analysis. Their photophysical properties have been further investigated both experimentally and theoretically. The results revealed that significant enhancement of two-photon absorption cross section values were obtained for the cyclic dinuclear Zn(II) and Cd(II) complexes compared with their free ligands. Additionally, confocal microscopy and two-photon microscopy fluorescent imaging of MCF-7 cells labeled with two ligands and Zn(II) complexes reveal their potential applications as a biological fluorescent probe.

Synthesis and photophysical properties of doubly porphyrin-substituted cyanine dye

New porphyrin-(cyanine dye) composites, in which two porphyrins are bridged by a cyanine dye through triple bonds, were synthesized. In the UV-vis absorption spectra of the composites, the Soret band and Q-band were red-shifted to 436 and 575–640 nm, respectively. The absorption originating from the cyanine dye portion was also red-shifted from 710 nm to 764 nm, suggesting the expansion of πconjugation over the porphyrin and cyanine dye parts. Fluorescence studies suggested that energy transfer from the porphyrin portion to the cyanine dye moiety occurred. The fluorescence intensity decreased with increasing dielectric constants of solvents, suggesting intramolecular photoinduced electron transfer from the porphyrin to the cyanine dye parts. The effective two-photon absorption (2PA) cross-section values were measured using a nanosecond open aperture Z-scan method. The maximum effective 2PA cross-section and two-photon excited fluorescence cross-section values were 33,000 GM and 4,800 GM, respectively, at 860 nm in toluene/pyridine (95:5).

Experimental and theoretical study of two-photon absorption in nitrofuran derivatives: Promising compounds for photochemotherapy

We report experimental and theoretical studies of the two-photon absorption spectrum of two nitrofuran derivatives: nitrofurantoine, (1-(5-nitro-2-furfurilideneamine)-hidantoine) and quinifuryl, 2-(5(')-nitro-2(')-furanyl)ethenyl-4-{N-[4(')-(N,N-diethylamino)-1(')-methylbutyl]carbamoyl} quinoline. Both molecules are representative of a family of 5-nitrofuran-ethenyl-quinoline drugs that have been demonstrated to display high toxicity to various species of transformed cells in the dark. We determine the two-photon absorption cross-section for both compounds, from 560 to 880 nm, which present peak values of 64 GM for quinifuryl and 20 GM for nitrofurantoine (1 GM = 1×10(-50)cm(4).s.photon(-1)). Besides, theoretical calculations employing the linear and quadratic response functions were carried out at the density functional theory level to aid the interpretations of the experimental results. The theoretical results yielded oscillator strengths, two-photon transition probabilities, and transition energies, which are in good agreement with the experimental data. A higher number of allowed electronic transitions was identified for quinifuryl in comparison to nitrofurantoine by the theoretical calculations. Due to the planar structure of both compounds, the differences in the two-photon absorption cross-section values are a consequence of their distinct conjugation lengths.

Synthesis and Characterizations of Star-Shaped Octupolar Triazatruxenes-Based Two-Photon Absorption Chromophores

A series of star-shaped octupolar triazatruxenes (TATs, 1-6) with intramolecular "push-pull" structure were synthesized and their photophysical properties have been systematically investigated. These chromophores showed obvious solvatochromic effect, i.e., significant bathochromic shift of the emission spectra and larger Stokes shifts were observed in more polar solvents mainly due to photoinduced intramolecular charge transfer (ICT). The two-photon absorption (2PA) cross-section values were determined by two-photon excited fluorescence (2PEF) measurements in toluene and THF. These chromophores exhibited large two-photon absorption cross-sections ranging from 280 to 1620 GM in the near-infrared (NIR) region. Compound 6 showed the largest 2PA action cross-section (σ(2)Φ) of 564 GM and could be a potential two-photon fluorescent (2PF) probe. In addition, compounds 1-6 all displayed good thermal stability and photostability.

Multipolar symmetric squaraines with large two-photon absorption cross-sections in the NIR region

The two-photon absorption (TPA) properties of two extended symmetric squaraine dyes are thoroughly characterized from the experimental and quantum-chemical point of view. The two molecules are specially engineered to have a multipolar structure with increasing complexity, D-π-A-π-D and A'-π-D-π-A-π-D-π-A', respectively. The experimental TPA spectra, measured by means of the Z-scan technique in the femtoseconds regime, display considerably high values of TPA cross sections (σ(TPA)) for both molecules. In particular, the squaraine with the more extended structure shows the highest value of σ(TPA) ever reported for this class of molecules. CIS and TDDFT calculations of the one and two-photon absorption properties are carried out to clarify the origin of the observed TPA properties and fully characterize the electronic properties of these compounds. The calculations, in good agreement with the experimental data, suggest that the origin of this exceptionally high σ(TPA) can be ascribed to the presence of a peripheral A' group, that increases the density of excited states involved in the TPA process.

Solution‐Processed Bulk‐Heterojunction Photovoltaic Cells Based on Dendritic and Star‐Shaped D‐π‐A Organic Dyes

A series of D-pi-A organic dendritic and star-shaped molecules based on three various chromophores (i.e., the truxene nodes, triphenylamine moieties as the donor, and benzothiadiazole chromophore as the acceptor) and their corresponding model compounds are facilely developed. Their photophysical and electrochemical properties are investigated in detail by UV/Vis absorption and photoluminescent spectroscopy, and cyclic voltammetry. By changing the various conjugated spacers (i.e., single bond, double bond, and triple bond) among the three chromophores of dendritic series, their photophysical properties (that is, the one-photon absorption range and two-photon absorption cross-section values) are effectively modulated. All D-pi-A conjugated oligomers show a broad and strong absorption band from 250 to 700 nm in thin films. Solution-processed bulk-heterojunction photovoltaic devices using our oligomer as donor and PCBM as acceptor are fabricated and measured. The power conversion efficiency of the devices based on our oligomers continuously increases from DBTTr to TrTD2A as a result of an increasing relative absorption intensity in longer wavelength region by changing the donor-acceptor ratio and conjugated spacers between the donor and acceptor. The power conversion efficiency of the devices based on TrTD2A was 0.54% under the illumination of AM 1.5 and 100 mW cm(-2), which is the highest value recorded based on D-pi-A conjugated oligomers containing triphenylamine moieties and benzothiadiazole chromophores with truxene to date.

Styryl Dyes as Two-Photon Excited Fluorescent Probes for DNA Detection and Two-Photon Laser Scanning Fluorescence Microscopy of Living Cells

Spectral-fluorescent properties of benzothiazole styryl monomer (Bos-3) and homodimer (DBos-21) dyes in presence of DNA were studied. The dyes enhance their fluorescence intensity in 2-3 orders of magnitude upon interaction with DNA. Studied styrylcyanines in DNA presence demonstrate rather high values of two-photon absorption (TPA) cross-section, which are comparable with the values of TPA cross section of the rhodamine dyes. An applicability of the styrylcyanines as probes for the fluorescence microscopy of living cells was studied. It was shown that both dyes are cell-permeable but homodimer dye DBos-21 produces noticeably brighter staining of HeLa cells comparing with monomer dye Bos-3. Molecules of DBos-21 initially bind to the nucleic acids-containing cell organelles (presumable mitochondria) and are able to penetrate into the cell nucleus. Thus, homodimer styryl DBos-21 dye is viewed as efficient stain for single-photon and two-photon excitation fluorescence imaging of living cells.

Protonated [4n]π and [4n+2]π Octaphyrins Choose Their Möbius/Hückel Aromatic Topology

Protonation-triggered conformational changes of meso-octakis(pentafluorophenyl) [36]octaphyrin and [38]octaphyrin have been investigated. The X-ray crystal structures and (1)H NMR analyses revealed that the protonation process cuts off intramolecular hydrogen bonds between aminic and iminic pyrrole units and, at the same time, produces intermolecular hydrogen-bond network between aminic pyrrole unit and counter-anions. Such a replacement induces some pyrrole inversion, leading to Mobius aromatic conformation for [36]octaphyrin and to Huckel aromatic conformation for [38]octaphyrin. These protonated octaphyrins show similar structures only with a subtle difference in tilted pyrrole angles, which results in their different topologies. This feature strongly suggests that the macrocycles control their topologies by pyrrole rotation to gain [4n]pi Mobius or [4n+2]pi Huckel aromatic stabilization, depending on the number of pi-electrons. Detailed photophysical properties such as absorption/fluorescence, excited singlet/triplet state lifetimes, and two-photon absorption cross-section values have been presented for both protonated [36] and [38]octaphyrins in conjunction with their Mobius or Huckel aromaticity.

Two-Photon Absorption Property of a Conjugated Polymer: Influence of Solvent and Concentration on Its Property

The Suzuki coupling reaction was utilized to prepare target conjugated polymer P1, whose main chain consists of 3,5-dicyanopyridine moieties as electron acceptors and both triphenylamino groups and fluorene moieties as donors. This polymer exhibits excellent solubility in organic solvents and high thermal stability (5% of weight loss at 398 degrees C). Detailed spectroscopic studies including absorption and fluorescence emission in solvents of different polarity were also conducted. The influence of the solvent and concentration on its two-photon absorption (TPA) property was studied by a two-photon-induced fluorescence (TPIF) method. It was found that the highest two-photon absorption cross section (13,260 GM at a laser wavelength of 940 nm) appeared in 1,2-dichloroethane, a solvent with a moderate polarity. Meanwhile, with the increase of its concentration in chloroform, its TPA cross section value is reduced, implying that its two-photon absorption process in its chloroform solution is not a pure intrachain process.

Versatile Photophysical Properties of meso‐Aryl‐Substituted Subporphyrins: Dipolar and Octupolar Charge‐Transfer Interactions

Donor-acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso-phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge-transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent-polarity-dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry-broken, and relaxed excited states, whereas the non-solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso-(4-aminophenyl) rotation at low temperature prevents the intramolecular charge-transfer (ICT)-forming process. The two-photon absorption (TPA) cross-section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross-section value of approximately 3200 GM (1 GM = 10(-50) cm(4) s photon(-1)) with donor-acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found between the electron-donating/-withdrawing abilities of the peripheral groups and the TPA cross-section values, that is, p-aminophenyl > m-aminophenyl > nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross-section value by a factor of approximately 2 and 4, respectively, for p-amino- and m-nitrophenyl-substituted subporphyrins. On the other hand, the stabilization of the symmetry-broken, dipolar ICT state gives rise to a negligible impact on the TPA processes.

π‐Conjugation Enlargement Toward the Creation of Multi‐Porphyrinic Systems with Large Two‐Photon Absorption Properties

Recent progress in the synthesis of covalently linked porphyrin arrays with large two-Photon absorption (TPA) cross-section values has been reviewed with a particular focus on the relation of TPA properties with molecular structures. Covalently linked porphyrin arrays continue to be important and useful for the creation of functional materials owing to their chemical robustness, fine-tuning, and easy manipulation. More importantly, the porphyrin electronic systems are quite susceptible to periphery conjugative perturbations, hence allowing facile fabrications to extensively delocalized systems. This property has been used for exploration of porphyrin-based molecular systems with large TPA values, demonstrating a general trend that enhancement in electronic interactions leads to large TPA cross-section values. As a representative example, the porphyrin tapes exhibit larger TPA values owing to the fully delocalized nature of the pi-electrons. This Focus Review will help understand the structural requirements of porphyrin arrays with large TPA values, which will be useful for future applications in optical communication in the IR region.

新型双光子吸收生色分子的电化学、热性能和光物理性质

Electrochemical, thermal, and photophysical properties of novel two- (BPODPA), four- (BBPOPA), and six-branch (TBPOA) triphenylamine chromophores are studied. The decomposition temperature of chromophores reaches 373-412 C. The electrochemical properties is explored by cyclic voltammetry. The ionization potential of chromophores is in the range of 5.14-5.18 eV. Excitation at 400 nm reveals emission peaks at 483-487 nm and the fluorescence quantum yields are 0.73-0.75 in CH2Cl2 Two-photon absorption (TPA) properties of chromophores are measured by nonlinear transmission method. The maximum TPA cross-section values are measured at 758 nm to be 20369 GM (1 GM=10^{-50} cm4s/photon) for TBPOA, 7024 GM for BBPOPA, and 1227 GM for BPODPA, respectively. When pumped with 800-nm laser irradiation, chromophores show strong two-photon excited blue-green fluorescence at 502-518 nm. These results provide a basis for understanding the electronic and optical properties of the conjugated multi-branch chromophore in terms of the underlying molecular and electronic structures.

Design of Dipicolinic Acid Ligands for the Two-Photon Sensitized Luminescence of Europium Complexes with Optimized Cross-Sections

The multistep synthesis of an extensive series of push-pull donor-pi-conjugated dipicolinic acid ligands is described. The charge transfer character of the ligand can be tuned by changing the donor group (CH 2R, OR, SR, or NR 2) or the nature of the conjugated backbone (phenyl, phenylethynyl, naphtylethynyl, bis(phenylethynyl), or chalcone). The photophysical properties of related D 3 symmetric europium complexes (absorption and luminescence) were measured. Experiments using two-photon sensitized luminescence of a Eu (III) complex reveal large two-photon absorption (TPA) cross-section values (775 GM at 740 nm) in dichloromethane. Furthermore, some structure-property relationships can be derived from this systematic study, allowing an optimization of TPA properties of lanthanide complexes.

Synthesis and Characterization of Two-Photon Absorbing Dithienothiophene Derivative with Silyl End Group

Efficient two-photon absorbing chromophore based on dithienothiophene has been synthesized and its two-photon absorption cross section (σ2) was evaluated by two-photon induced fluorescence excitation spectroscopy. The chromophore obtained shows a sizable two-photon absorption cross section value of 618 GM at 700 nm. By using one- and two-photon spectroscopic experiment, two-photon absorption properties of the chromophore with the electronic transition dipole moment and one- and two-photon transition energies were evaluated. Besides, we have demonstrated the successful application of this compound in fabrication of 2D and 3D microobjects by using two-photon microfabrication technique.