Strong, low-energy two-photon absorption in extended amine-terminated cyano-substituted phenylenevinylene oligomers

Three quadrupolar oligophenylenevinylenes with five rings in the conjugated backbone, terminal donor groups, and various acceptors and/or donors along the backbone were synthesized and their two-photon spectroscopic properties investigated. These chromophores exhibit large two-photon absorption cross sections over a wide wavelength range and two distinct peaks, the strongest of which (deltamax > 3600 GM) is observed at 960-970 nm, a wavelength close to twice the value of the linear absorption maximum (2lambda(1)max). The findings on these chromophores are compared with those for analogous molecules with shorter conjugation length, for which the main two-photon band is at significantly shorter wavelength than 2lambda(1)max.     

Two-photon photosensitized production of singlet oxygen: optical and optoacoustic characterization of absolute two-photon absorption cross sections for standard sensitizers in different solvents

Singlet molecular oxygen, O2(a1Deltag), can be produced upon resonant two-photon excitation of a photosensitizer. In the present study, two molecules that have received recent attention in studies of nonlinear organic materials were characterized for use as standard two-photon sensitizers: 2,5-dicyano-1,4-bis(2-(4-diphenylaminophenyl)vinyl)-benzene, CNPhVB, and 2,5-dibromo-1,4-bis(2-(4-diphenylaminophenyl)vinyl)-benzene, BrPhVB. Absolute two-photon absorption cross sections, delta, were independently determined for these molecules using two techniques that have heretofore not been applied to this problem: an optical technique (time-resolved detection of O2(a1Deltag) phosphorescence) and a nonoptical technique (a time-resolved laser-induced optoacoustic experiment). For experiments performed in toluene, a solvent commonly used for such nonlinear optical studies, appreciable absorption by the solvent itself complicates the measurements. In cyclohexane, however, delta values could be obtained without the interfering effects of solvent absorption. On the basis of these results, we discuss key aspects of the respective techniques used to quantify values of delta. The information reported herein provides some explanation for the lack of consensus that is routinely observed in published values of delta, certainly for experiments performed in aromatic solvents such as toluene and benzene.     

Boron-containing two-photon-absorbing chromophores. 3. One- and two-photon photophysical properties of p-carborane-containing fluorescent bioprobes

Boron-containing two-photon-absorbing fluorophores have been prepared as new bifunctional molecules, potentially useful in two-photon excited microscopy (TPEM) and boron neutron capture therapy. They are based on a one-dimensional conjugated system containing a p-carborane entity at one end of the molecule and various electron-donating groups containing oxygen or nitrogen atoms at the other end. We investigated their one- and two-photon photophysical properties. They showed efficient fluorescence in an organic solvent, as well as in water for two of them, allowing microscopy on cell cultures. High two-photon absorption cross sections were determined in the 700-900 nm range. TPEM images were obtained with these new p-carborane-containing fluorophores, with laser intensities in the submilliwatt range.     

Synthesis and photophysical properties of novel pyrimidine-based two-photon absorption chromophores

Three new two-photon absorption chromophores based on a pyrimidine core were synthesized by Aldol condensation in the absence of any organic solvents. Their single-photon spectroscopic characterization as well as their two-photon absorption properties is reported. In addition, strong modulation of single-photon and two-photon fluorescent spectra of these molecules by (de)protonation is also discussed.     

Polyethylene glycol-functionalized benzylidene cyclopentanone dyes for two-photon excited photodynamic therapy

A series of polyethylene glycol-functionalized benzylidene cyclopentanone dyes with varying lipid/water partition coefficients were synthesized in high yields by a simple process. Detailed characterization and systematic studies of these molecules, including linear and nonlinear photophysical properties, reactive oxygen yields, and in vitro photodynamic therapy (PDT) activities, were conducted. Four of these dyes exhibited good solubility in PBS (>2 mg ml(-1), which is sufficient for clinical venous injection), high reactive oxygen yields, large two-photon absorption and low dark toxicity, under the therapy dosage. Among them, two dyes could be absorbed efficiently by human rectal cancer 1116 cells, and presented strong two-photon excited PDT activity in in vitro cell experiments.     

苯并噻唑衍物的合成及结构-双光子吸收光物理特性关系

报道了三个具有典型A-π-A'型共轭结构的苯并噻唑衍生物的合成及结构-双光 子吸收光物理特性关系。通过对三个化合物的共轭结构增长和拉电子基强度变化对 化合物单光子荧光光谱、双光子诱导荧光光谱和双光子吸收截面等特性的影响研究 ，我们发现，苯并噻唑杂环中的杂原子硫在化合物共轭链链短时对其光物理特性影 响很强，在共轭链较长时影响减弱甚至消失。通常情况下，共轭链长度和拉电子基 强度共同对双光子吸收截面作贡献，我们的研究表明，当共轭链较长时，共轭链的 增长对增强分子双光子吸收截面的贡献远大于拉电子基强度变化的贡献。其中，新 化合物2（2-{4-[2-（4-硝基苯基）-乙烯基]苯基}-乙烯基）苯并噻唑具有双光子 吸收截面大(181*10~(-50)cm~4s/photon)和荧光量子产率高(13.8%)的特点，是双 光子荧光显微与成像应用的一个良好的候选材料。     

One- and two-photon absorptions in asymmetrically substituted free-base porphyrins: a density functional theory study

Electronic spectra and structures of a new family of free-base porphyrin (H(2)P) derivatives with 4-(diphenylamino)stilbene (DPAS) or 4,4'-bis-(diphenylamino)stilbene (BDPAS) asymmetric substituents, recently synthesized and studied by Drobizhev et al. [J. Phys. Chem. B 110, 9802 (2006)] are investigated by density functional theory (DFT) using modern density functionals and the 6-31G* basis set. The time-dependent DFT technique is applied for calculations of one- and two-photon absorption spectra, electric and magnetic dipole moments, and for prediction of electronic circular dichroism for these chiral molecules. The four-band absorption spectrum of the H(2)P molecule (Q(x), Q(y), 0-0 and 1-0 bands) is enhanced in single-bond-linked DPAS. This enhancement is explained by hyperconjugation of the almost orthogonal pi systems and by small charge-transfer admixtures. The effect is much stronger for the double-bond- and triple-bond-linked DPAS and BDPAS substituents where absorption in the Q region transforms into a two-band spectrum. These molecules with ethenyl and ethynyl bonding of the porphyrin and donor substituent show very strong two-photon absorption in the near-infrared region. DFT calculations explain this by more efficient conjugation between the H(2)P and DPAS (BDPAS) chromophores, since they are almost coplanar: "Gerade" states of the H(2)P molecule occur in the Soret region and transform into charge-transfer states with nonzero transition moments. They are responsible for the strong two-photon absorption effects. Mixing of excitations in both chromophores explains the broadening of the Soret band. Though the calculated two-photon absorption cross sections are overestimated, the qualitative trends are reproduced and help understanding the whole genesis of spectra of these asymmetrically substituted H(2)P derivatives.     

多枝[1,3,4]-噁二唑衍生物的双光子吸收和光功率限幅特性

采用非线性透过率法测定了多枝[1,3,4]-噁二唑衍生物的双光子吸收性质. 测定了化合物的单光子荧光光谱和双光子荧光光谱, 在800 nm波长的激光激发下, 9-乙基-3,6-双{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基}-咔唑(3)和三-{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基-4-苯基}-胺(4)能够发出很强的蓝色和黄绿色双光子上转换荧光, 荧光峰分别位于485和547 nm. 这些多枝结构化合物的双光子吸收截面较大(数值超过104 GM), 并具有很强的光限幅效应. 多枝分子中重复单元的推拉电子结构和协同效应有效地增强了分子的双光子吸收性质.     

Effects of conjugation length and resonance enhancement on two-photon absorption in phenylene-vinylene oligomers

Two-photon excitation spectra have been recorded over the large spectral range of 540-1000 nm for five phenylene-vinylene oligomers that differ in the length of the conjugated pi system. The significant changes observed in the two-photon excitation spectra and absorption cross sections as a function of this systematic change in the chromophore are discussed in light of (1) the corresponding one-photon absorption spectra and (2) high-level density functional response theory calculations performed on analogues of these systems. The results obtained illustrate one way to exploit parameters that influence nonlinear optical properties in large organic molecules. Specifically, data are provided to indicate that when the frequency of the laser used in the two-photon experiment is nearly-resonant with an allowed one-photon transition, significant increases in the two-photon absorption cross section can be realized. This phenomenon of the so-called resonance enhancement allows for greater control in obtaining an optimal response when using existing two-photon chromophores, and provides a much-needed guide for the systematic development and efficient use of two-photon singlet oxygen sensitizers.     

Two-photon absorption of metal-organic DNA-probes

We report remarkable multiphoton absorption properties of DNA intercalating ruthenium complexes: (1) [Ru(phen)(2)dppz](2+); (2) [(11,11'-bidppz)(phen)(4)Ru(2)](4+); (3) [11,11'-bipb(phen)(4)Ru(2)](4+). Two-photon spectra in the range from 460 to 1100 nm were measured using the Z-scan technique. In particular, complex 2 was found to exhibit very strong two- and three-photon absorption properties, which could be an effect of symmetric charge transfer from the ends towards the middle of the conjugated dimeric orbital system. We propose that these molecules could provide a new generation of DNA binding nonlinear chromophores for wide applications in biology and material science. The combination of a large two-photon cross section and strong luminescence quantum yields for the molecules when intercalated makes the compounds uniquely bright and photo-stable probes for two-photon luminescence imaging and also promising as enhanced photosensitizers in two-photon sensitizing applications.     

Two-photon absorption in three-dimensional chromophores based on [2.2]-paracyclophane

A series of alpha,omega-bis donor substituted oligophenylenevinylene dimers held together by the [2.2]paracyclophane core were synthesized to probe how the number of repeat units and through-space delocalization influence two-photon absorption cross sections. Specifically, the paracyclophane molecules are tetra(4,7,12,15)-(4'-dihexylaminostyryl)[2.2]paracyclophane (3R(D)), tetra(4,7,12,15)-(4' '-(4'-dihexylaminostyryl)styryl)[2.2]paracyclophane (5R(D)), and tetra(4,7,12,15)-(4' "-(4' '-(4'-dihexylaminostyryl)styryl)styryl)[2.2]paracyclophane (7R(D)). The compounds bis(1,4)-(4'-dihexylaminostyryl)benzene (3R) and bis(1,4)-(4' '-(4'-dihexylaminostyryl)styryl)benzene (5R) were also synthesized to reveal the properties of the "monomeric" counterparts. The two-photon absorption cross sections were determined by the two-photon induced fluorescence method using both femtosecond and nanosecond pulsed lasers as excitation sources. While there is a red shift in the linear absorption spectra when going from the "monomer" chromophore to the paracyclophane "dimer" (i.e., 3R --> 3R(D), 5R --> 5R(D)), there is no shift in the two-photon absorption maxima. A theoretical treatment of these trends and the dependence of transition dipole moments on molecular structure rely on calculations that interfaced time-dependent density functional theory (TDDFT) techniques with the collective electronic oscillator (CEO) program. These theoretical and experimental results indicate that intermolecular interactions can strongly affect B(u) states but weakly perturb A(g) states, due to the small dipole-dipole coupling between A(g) states on the chromophores in the dimer.     

末端基团对芴类衍生物分子非线性光学性质的影响

通过采用预估矫正的时域有限差分方法数值求解速率方程-光场强度方程,研究了纳秒激光脉冲在具有不同末端基团的对称性芴类衍生物分子2,7-双(4′-(二甲基氨基)苯乙烯基)-9-氢-芴(F1分子)和2,7-双(4′-硝基苯乙烯基)-9-氢-芴(F2分子)中的动力学传播过程以及光限幅效应,分析了两种分子的光限幅特性随传播距离(z)、粒子数密度(N)以及脉冲宽度(τ)的变化情况,并且拟合了两种分子的动态双光子吸收(TPA)截面。计算结果表明,该系列分子具有较大的双光子吸收截面以及较好的光限幅效应。此外,F2分子的末端基团―NO2与F1分子的末端基团―N(CH3)2相比具有更强的得电子能力,因而使得F2分子具有更大的跃迁偶极矩,双光子吸收截面增大,光限幅效应更为明显。     

Two-photon absorption strength: a new tool for the quantification of two-photon absorption

In this paper, we define the two-photon absorption strength, a new characterization tool, similar to the oscillator strength, but for two-photon absorption. It allows the quantification of the two-photon absorption properties of molecular systems which are one-photon transparent. Its definition is such that the corresponding numerical values are around 100 for small molecules. We also show that this new theoretical tool allows the direct comparison of experimental and theoretical data without requiring the introduction of any arbitrary band width. As an example, the experimental and theoretical (AM1+CNDOS and HF+CIS3-21G) two-photon absorption properties of the 2,2'-bi(9,9-dihexylfluorene) molecule are compared.     

Two-photon absorption cross sections: an investigation of the accuracy of calculated absolute and relative values

We have studied the basis set and electron correlation effects on the ab initio calculations of two-photon absorption cross sections of water. Various series of correlation consistent basis sets up to triply augmented basis sets of valence pentuple zeta level as well as the popular 6-31G(d) basis set have been employed in combination with several coupled cluster, configuration interaction, and density functional theory methods. We find that it is very difficult to obtain converged values of the cross sections for even a small molecule such as water. Acknowledging these difficulties in obtaining a fully converged cross section for a given state, we also investigated the possibility of determining relative cross sections for a series of organic molecules. However, we did not find consistency between the relative cross sections calculated at the Hartree-Fock level and several coupled-cluster methods using the 6-31G(d) and aug-cc-pVDZ basis sets. However, we could reproduce the relative ordering of the two-photon absorption cross sections of the molecules studied at the Hartree-Fock level.     

Nonlinear optical and two-photon absorbtion properties of 1,3,5-tricyano-2,4,6-tris(styryl)benzene-containing octupolar oligomers

Octupolar oligomers containing 2-12 molecules of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives have been synthesized and their nonlinear optical and two-photon absorption (TPA) properties were determined. The beta(0) values are in the range of (85-1219) x 10(-30) esu and increase monotonically with the increasing number of the octupolar units within the molecule. The two-photon-induced fluorescence excitation spectra are quite similar to the single-photon absorption spectra except that the wavelength is doubled, indicating that the one- and two-photon allowed excited states are the same. The peak TPA cross-section values (delta(max)) measured with nanosecond pulses by the two-photon-induced fluorescence method are in the range (3010-62, 930) x 10(-50) cm(4)s photon(-1). The delta(max) increases as the number of the octupolar units in the molecules increases. A linear relationship is observed between delta(max) and beta, and this delta-beta relationship serves as a useful design strategy for the synthesis of novel octupolar oligomers and polymers with large TPA and beta.     

Ultrafast excited state dynamics of modified phthalocyanines: p-HPcZn and p-HPcCo

Two modified metallophthalocyanines (MPcs) containing sulfonic naphthoxy substituents were synthesized. The measurements of transient absorption and time-resolved photoluminescence were used to study the ultrafast response and excited state dynamics of two MPcs in dimethyl sulfoxide (DMSO) solution, which were predominantly in the monomeric form. Under excitation at 400 nm, these molecules experience vibrational relaxation to the bottom of the first excited state and then the excitation rapidly converts to the low-lying charge-transfer (CT) state and finally reaches the triplet states. Under excitation at 800 nm, they show a two-photon absorption character, and their excited state dynamics exhibit strong dependence on the probe wavelength. The main results with 400 nm pumping are similar to the results with 800 nm pumping. For p-HPcZn, weak two-photon photoluminescence was also observed with a lifetime of 52 +/- 2 ps. A four-level model was used to illustrate the excited state dynamics of p-HPcZn, while a five-level model was suggested for p-HPcCo molecule.     

Synthesis,structure and nonlinear optical properties of two novel two-photon absorption chromophores

Two triphenylamine-based derivatives that can be used as two-photon absorption chromophore,tris{4-[4-(3-trifluoromethyl-3-oxopanoyl)]phenyl}amine (1) and tris{4-[4-(3-phenyl-3-oxopanoyl)] phenyl} amine (2) were successfully synthesized and fully characterized by elemental analysis,IR,1H NMR and MS. The single crystal X-ray diffraction analysis showed that the molecules possess D-(π-A)3 structures. One-and two-photon absorption and fluorescence in various solvents were experimentally investigated. A data rec...     

Two-photon absorption and first nonlinear optical properties of ionic octupolar molecules: structure-function relationships and solvent effects

We present a quantum-chemical analysis of the two-photon absorption properties and first hyperpolarizabilities of a series of ionic octupolar molecules and a comparison of their characteristics with corresponding neutral molecules. The molecular geometries are obtained via BL3YP/6-31G (d,p) level optimization including the SCRF/PCM approach, while the dynamic NLO and two-photon absorption properties are calculated with the ZINDO/CV method including solvent effects. The effects of donor or acceptor substitution and elongation of the conjugation path length are established to demonstrate the engineering guidelines for enhancing two-photon absorption cross section and molecular optical nonlinearities. It is found that the chain length dependence of the two-photon absorption and the first nonlinearity follow the same trend, displaying a saturation limit at n = 5. The solvent induced effect on the two-photon absorption and NLO properties are studied using the ZINDO/CV/SCRF method. It has been observed that two-photon absorption and the first nonlinearity peaks at epsilon approximately = 20 and then decreases slightly, approaching saturation. We also compare our theoretical findings with the experimental results wherever available in the literature.     

基于咔唑的双光子荧光次氯酸根探针光学性质及响应机理

采用含时密度泛函理论与响应函数理论相结合的方法,研究了两种实验室新合成的水溶性双光子荧光次氯酸根（ClO^-）探针分子HCH和HCM的单光子吸收、双光子吸收和荧光发射性质。计算结果表明,HCH和HCM分子与ClO^-反应后,生成物的光吸收和光发射性质均发生明显变化,相应的吸收和发射峰位都发生了明显蓝移,荧光强度展现出明显的增强。另外,两探针分子都具有较大的双光子吸收截面,且与ClO^-反应后,生成物的双光子吸收截面值显著增加,因此两分子均可作为性能优良的双光子荧光探针分子。此外,通过分析HCH和HCM分子与ClO^-反应前后的Mulliken电荷布居情况,从理论上证实了该系列荧光探针分子的识别机理是C＝N异构化。     

Diaroyl(methanato)boron difluoride compounds as medium-sensitive two-photon fluorescent probes

This paper evaluates the use of diaroyl(methanato)boron difluoride compounds for designing efficient fluorescent probes through two-photon absorption. Three different pathways allowing for the syntheses of symmetrical and dissymmetrical molecules are reported. The stable diaroyl(methanato)boron difluoride derivatives can be easily obtained in good yields. They exhibit a large one-photon absorption that is easily tuned in the near-UV range. Their strong fluorescence emission covers the whole visible domain. In addition to these attractive linear properties, several diaroyl(methanato)boron difluoride derivatives possess significant cross sections for two-photon absorption. The derived structure-property relationships are promising for designing new generations of molecules relying on the diaroyl(methanato)boron difluoride backbone.