Platinum acetylide two-photon chromophores

To explore the photophysics of platinum acetylide chromophores with strong two-photon absorption cross-sections, we have investigated the synthesis and spectroscopic characterization of a series of platinum acetylide complexes that feature highly pi-conjugated ligands substituted with pi-donor or -acceptor moieties. The molecules (numbered 1-4) considered in the present work are analogs of bis(phenylethynyl)bis(tributylphosphine)platinum(II) complexes. Molecule 1 carries two alkynyl-benzothiazolylfluorene ligands, and molecule 2 has two alkynyl-diphenylaminofluorene ligands bound to the central platinum atom. Compounds 3 and 4 possess two dihexylaminophenyl substituents at their ends and differ by the number of platinum atoms in the oligomer "core" (one vs two in 3 and 4, respectively). The ligands have strong effective two-photon absorption cross-sections, while the heavy metal platinum centers give rise to efficient intersystem crossing to long-lived triplet states. Ultrafast transient absorption and emission spectra demonstrate that one-photon excitation of the chromophores produces an S1 state delocalized across the two conjugated ligands, with weak (excitonic) coupling through the platinum centers. Intersystem crossing occurs rapidly (Kisc approximately 1011 s-1) to produce the T1 state, which is possibly localized on a single conjugated fluorenyl ligand. The triplet state is strongly absorbing (epsilonTT > 5 x 104 M-1 cm-1), and it is very long-lived (tau > 100 micro s). Femtosecond pulses were used to characterize the two-photon absorption properties of the complexes, and all of the chromophores are relatively efficient two-photon absorbers in the visible and near-infrared region of the spectrum (600-800 nm). The complexes exhibit maximum two-photon absorption at a shorter wavelength than 2lambda for the one-photon band, consistent with the dominant two-photon transition arising from a two-photon-allowed gerade-gerade transition. Nanosecond transient absorption experiments carried out on several of the complexes with excitation at 803 nm confirm that the long-lived triplet state can be produced efficiently via a sequence involving two-photon excitation to produce S1, followed by intersystem crossing to produce T1.     

An iridium(III) complex that exhibits dual mechanism nonlinear absorption

The photophysical properties of the complex (L)Ir(ppy)(2)(+), where ppy = 2-phenylpyridine and L = 4,4'-(2,2'-bipyridine-5,5'-diylbis(ethyne-2,1-diyl))bis(N,N-dihexylaniline), have been investigated under one- and two-photon excitation conditions. In THF solution, the complex exhibits broad ground-state absorption with lambda(max) approximately 500 nm and weak photoluminescence with lambda(max) approximately 730 nm. Excitation of (L)Ir(ppy)(2)(+) at 355 nm produces a long-lived excited state (tau approximately 1 mus) that features a strong excited-state absorption in the near-infrared (lambda(max) approximately 875 nm, Deltaepsilon approximately 6.1 x 10(4) M(-1) cm(-1)). Photoluminescence and transient absorption studies of (L)Ir(ppy)(2)(+) carried out using 5 ns, 1064 nm pulsed excitation demonstrate that the same long-lived and strongly absorbing excited state can be efficiently produced by two-photon absorption. Solutions of the complex in THF display nonlinear absorption of 5 ns, 1064 nm pulses in a process that is believed to involve a combination of two-photon absorption and reverse saturable absorption.     

Two-photon absorption properties of 2,6-bis(styryl)anthracene derivatives: effects of donor-acceptor substituents and the pi center

A series of 2,6- and 2,7-bis(styryl)anthracene derivatives with the donors at the styryl group and acceptors at the 9,10-positions have been synthesized, and their two-photon cross sections (Phidelta(max)) were determined. These compounds exhibit a peak two-photon absorptivity (delta(max)) in the range of 700-2500 GM at 780-1030 nm. Values of lambda(max) and Stokes shifts increase as the acceptor is changed to a stronger one. There is also a parallel increase in lambda(2)max and delta(max) with the same variation of the chromophore structure. Both lambda (2)(max)and Phidelta(max) have been optimized by introducing donor-substituted styryl groups at the 2,6-positions and p-cyanophenyl groups at the 9,10-positions, respectively. The effect of a pi center on the two-photon absorption properties has been assessed by comparing the existing data for a variety of D-pi-D derivatives.     

Hyper-Rayleigh scattering measurements of nonlinear optical chromophores at 1907 nm

Hyper-Rayleigh scattering measurements are performed on nonlinear optical chromophores using an excitation wavelength of 1907 nm. This wavelength is the longest that has yet been reported for the hyper-Rayleigh scattering experiment and allows measurements of the first hyperpolarizability of chromophores that are free of contributions from two-photon absorption induced fluorescence and reduces one and two photon resonance enhancement to a minimum. Using the 1907 nm setup we demonstrate good agreement between our results and those obtained with the electric field induced second harmonic generation (EFISHG) technique previously performed at this wavelength.     

Energy and electron transfer in enhanced two-photon-absorbing systems with triplet cores

Enhanced two-photon-absorbing (2PA) systems with triplet cores are currently under scrutiny for several biomedical applications, including photodynamic therapy (PDT) and two-photon microscopy of oxygen. The performance of so far developed molecules, however, is substantially below expected. In this study we take a detailed look at the processes occurring in these systems and propose ways to improve their performance. We focus on the interchromophore distance tuning as a means for optimization of two-photon sensors for oxygen. In these constructs, energy transfer from several 2PA chromophores is used to enhance the effective 2PA cross section of phosphorescent metalloporphyrins. Previous studies have indicated that intramolecular electron transfer (ET) can act as an effective quencher of phosphorescence, decreasing the overall sensor efficiency. We studied the interplay between 2PA, energy transfer, electron transfer, and phosphorescence emission using Rhodamine B-Pt tetrabenzoporphyrin (RhB-PtTBP) adducts as model compounds. 2PA cross sections (sigma2) of tetrabenzoporphyrins (TBPs) are in the range of several tens of GM units (near 800 nm), making TBPs superior 2PA chromophores compared to regular porphyrins (sigma2 values typically 1-2 GM). Relatively large 2PA cross sections of rhodamines (about 200 GM in 800-850 nm range) and their high photostabilities make them good candidates as 2PA antennae. Fluorescence of Rhodamine B (lambda(fl) = 590 nm, phi(fl) = 0.5 in EtOH) overlaps with the Q-band of phosphorescent PtTBP (lambda(abs) = 615 nm, epsilon = 98 000 M(-1) cm(-1), phi(p) approximately 0.1), suggesting that a significant amplification of the 2PA-induced phosphorescence via fluorescence resonance energy transfer (FRET) might occur. However, most of the excitation energy in RhB-PtTBP assemblies is consumed in several intramolecular ET processes. By installing rigid nonconducting decaproline spacers (Pro10) between RhB and PtTBP, the intramolecular ETs were suppressed, while the chromophores were kept within the F?rster r0 distance in order to maintain high FRET efficiency. The resulting assemblies exhibit linear amplification of their 2PA-induced phosphorescence upon increase in the number of 2PA antenna chromophores and show high oxygen sensitivity. We also have found that PtTBPs possess unexpectedly strong forbidden S0 --> T1 bands (lambda(max) = 762 nm, epsilon = 120 M-1 cm-1). The latter may overlap with the laser spectrum and lead to unwanted linear excitation.     

Synthesis and optical properties of all-trans-oligodiacetylenes

A new series of pure and highly soluble oligodiacetylenes (ODAs) was synthesized in high yield and on a multi-milligram scale by a sequence of Sonogashira reactions with a strongly reduced level of homocoupling. The lambda(max) and epsilon(max) of these ODAs show an increase with both chain elongation and solvent polarity. A plot of lambda(max) absorption versus 1/CL (CL=conjugation length) was shown to be linear. The lambda(max) converges to 435 nm for the longest members of the series at micromolar concentration. This reveals that the longest wavelength absorption observed for PDA chains (lambda(max) up to 700 nm) is due to aggregation effects. The fluorescence quantum yield increased from monomer to trimer and decreased for longer ODAs. A similar trend is found for the lifetime of fluorescence with a maximum of 600 ps for the trimer. The observed linearity of the rotational correlation time with the oligomer length implies that the ODA chains in solution lack significant geometrical changes. This implies that the ODAs in solution are fully stretched molecular rods of up to 4 nm in length.     

1,3,4-噁二唑衍生物的双光子吸收和双光子泵浦荧光

依据“推电子基-共轭中心-拉电子基-共轭中心-推电子基”的模型将电荷传输型1,3,4-噁二唑环嵌入芳香共轭体中, 通过Wittig-Horner反应合成了2种对称型强双光子吸收和双光子诱导荧光分子2,5-二[4-(2-芳基乙烯基)苯基]-1,3,4-噁二唑. 它们的氯仿溶液在锁模Nd: YAG激光器800 nm激光照射下, 发射出很强的双光子上转换荧光, 其最强荧光分别在波长507和475 nm. 采用非线性透过率法测得其双光子吸收截面分别为1.07×10^－46和6.6×10^－47 cm⁴•s•photon^－1. 这2个对称型D-π-A-π-D生色分子从激发端基到π共轭桥的有效能量传输, 对双光子吸收和双光子荧光发射能力贡献较大.     

以N为耦合中心多枝分子的双光子上转换荧光

采用非线性透过率法研究了以N为耦合中心的多枝化合物N-[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}-N,N-二苯胺(BPODPA), N,N-双[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}-N-苯胺(BBPOPA)和N,N,N-三[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}-1-乙烯基}苯基}胺(TBPOA)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上转换荧光光谱, 研究了多枝化对三苯胺分子双光子吸收和双光子激发荧光性质的影响.在800 nm波长的激光激发下,化合物BPODPA、BBPOPA和TBPOA在二氯甲烷溶液中发出很强的蓝绿色双光子上转换荧光, 荧光峰分别位于502、515 和518 nm. 这些多枝结构化合物的双光子吸收截面较大, 双光子吸收增强来源于多枝分子中扩展的π共轭体系和重复单元的协同效应.     

Theoretical prediction of one- and two-photon absorption properties of N-annulated quaterrylenes as near-infrared chromophores

Graphene nanoribbons (GNRs) have attracted increasing attention due to high potentiality in nanoelectronics. In the present study, quantum-chemical calculations of structural and nonlinear optical properties have been first carried out for the nanoelectronical materials, a new series of ladder-type N-annulated quaterrylenes and their imide chromophores. The effects of the solvent, terminal groups, the number of N-annulated bridges, and π-conjugated length are discussed in detail. The solvent effect is significant on the one-photon absorption (OPA). Moreover, the OPA and two-photon absorption (TPA) properties of the two series of DI and N-MI molecules show a clear solvent dependence, which is attributed to the carboximide substitution featuring larger polarization. Introducing electron-donating groups and dicarboximides and increasing the conjugated length lead to red-shifts of the OPA, emission, and TPA spectra, lower emission lifetimes, and enhanced TPA cross sections (δ(max)), but further extension of the conjugated framework does not always promote an increase of δ(max). The changing trends of δ(max) can be explained by the transition moment and the intramolecular charge transfer. All N-annulated quaterrylene and their imide derivatives possess small energy gaps, intense near-infrared absorption and emission, and large δ(max), which are important for use as two-photon fluorescent labeling materials.     

Large two-photon absorptivity of hemoglobin in the infrared range of 780-880 nm

Porphyrin molecules have a highly conjugated cyclic structure and are theorized to have unusually large two-photon absorptivities (sigmaTPA), i.e., sigmaTPA approximately 10(2) GM. The authors tested this claim. Ultrafast two-photon absorption (TPA) spectroscopy was performed on solutions of hemoglobin, which contains a naturally occurring metaloporphyrin. They used a pump-probe technique to directly detect the change in transmission induced by TPA over the wavelength range of lambda0=780-880 nm. As controls, they measured the TPA of the dyes rhodamine 6G and B; their measurements both verify and extend previously reported values. In new results, hemoglobin was found to have a peak two-photon absorptivity of sigmaTPA approximately 150 GM at lambda0=825 nm, near a resonance of the Soret band. This value supports theoretical expectations. They also found a significant difference in the TPA of carboxyhemoglobin versus oxyhemoglobin, e.g., sigmaTPA=61 GM versus sigmaTPA=18 GM, respectively, at lambda0=850 nm, which shows that the ligand affects the electronic states involved in TPA.     

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.     

Two-photon absorption in aqueous micellar solutions

Addition of the surfactant sodium dodecyl sulfate at concentrations above the critical micelle concentration increases the fluorescence quantum yield and the two-photon absorption cross-section of charged [2.2]paracyclophane chromophores containing pairs of D-pi-D chromophores. The resulting spectra in the micellar solutions are very similar to those obtained for neutral isostructural analogues in toluene. The measured etadelta values are 1300 GM for 1C and 1920 GM for 2C, which are comparable or larger to those in toluene. These results highlight possible misleading interpretation of two-photon-induced emission for evaluating the concentration of labeled substrates used in two-photon microscopy and provide guidelines for designing molecular structures with optimized two-photon action cross-sections in water.     

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.     

Metal ion sensing novel calix[4]crown fluoroionophore with a two-photon absorption property

1,3-Alternate calix[4]arene-based fluorescent chemosensors bearing two-photon absorbing chromophores have been synthesized, and their sensing behaviors toward metal ions were investigated via absorption band shifts as well as one- and two-photon fluorescence changes. Free ligands absorb the light at 461 nm and weakly emit their fluorescence at 600 nm when excited by UV-vis radiation at 461 nm, but no two-photon excited fluorescence is emitted by excitation at 780 nm. Addition of an Al(3+) or Pb(2+) ion to a solution of the ligand causes a blue-shifted absorption and enhanced fluorescence due to a declined resonance energy transfer (RET) upon excitation by one- and two-photon processes. Addition of a Pb(2+) ion to a solution of 1.K(+) results in a higher fluorescence intensity than the original 1.Pb(2+) complex regardless of one- or two-photon excitation, due to the allosteric effect induced by the complexation of K(+) with a crown loop.     

Two photon absorption properties of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives

Two-photon absorption (TPA) properties of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives have been investigated. Comparison of the absorption and fluorescence spectra reveals that these compounds show large Stokes shifts, which increase gradually as the conjugation length increases. One-photon absorption and excitation spectra are similar except that the latter exhibit several peaks near lambda(max). It is also found that the one- and two-photon-induced fluorescence excitation spectra are quite similar, which indicates 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 (50-2620) x 10(-50) cm4 s/photon. The delta(max) value increases as the donor strength and conjugation length increase. A linear relationship is observed between delta(max) and beta, and this delta-beta relationship is found to serve as a useful synthetic strategy for the design of novel TPA dyes with the octupolar structure.     

Nonlinear optical chromophores with pyrrole moieties as the conjugated bridge: enhanced NLO effects and interesting optical behavior

A series of nonlinear optical (NLO) chromophores were successfully prepared, in which pyrrole moieties were the conjugated bridge. In comparison with their analogues containing furan or thiophene groups as the bridge, these chromophores demonstrated similar or enhanced NLO effects (up to 3.3 times) and interesting optical behavior. While the acceptor groups were malononitrile (Mal), 3-phenyl-5-isoxazolone (Iso), and 1,3-diethylthiobarbituric acid (Bar), the chromophores exhibited much blue-shifted maximum absorption wavelengths (lambda max) (up to 36 nm); however, the lambda max of the chromophore containing tricyanovinyldihydrofuran (TCF) as acceptor became much longer than that of the analogue (up to 75 nm).     

Synthesis of C60-diphenylaminofluorene dyad with large 2PA cross-sections and efficient intramolecular two-photon energy transfer

The first, highly two-photon active C60 derivative comprised of a A-sp3-D conjugate structure was synthesized showing effective two-photon absorption cross-sections (sigma 2' = 196 x 10(-48) cm4 sec-1 molecule-1) in the nanosecond regime among the best values for diphenylaminofluorene-based AFX chromophores.     

A novel photochromic system of 4,5-dialkenylthiophenes constructed by the smarium diiodide promoted coupling reactions of thiophene-2-carboxylate with aryl ketones

[reaction: see text] The SmI2-promoted coupling reaction of ethyl thiophene-2-carboxylate with aryl ketones (2 equiv), followed by acid-catalyzed dehydration and oxidative aromatization, gave dialkenylthiophenes 1b-d, which underwent electrocyclizations upon irradiation with 300-nm light in CH3CN solution to give the corresponding closed-ring species with absorption lambda(max) approximately 425 nm. The interconversion between dialkenylthiophenes and their corresponding closed-ring species constitutes a novel photochromic system bearing an ester group for potential uses in linkage and wavelength tuning.     

Two-photon absorption properties of alkynyl-conjugated pyrene derivatives

A series of pyrene derivatives having 4-(N,N-dimethylamino)phenylethynyl groups as the substituent (1-5) have been synthesized and their two-photon absorption properties were investigated. Comparison of two-photon cross section (delta(max)) with related compounds reveals that pyrene is as efficient a pi-center as anthracene in two-photon materials. Moreover, the two-photon cross section (delta(max)) increased with the number of substituents reaching at the maximum value of 1150 GM for the tetra-substituted derivative (5). Furthermore, the two-photon action cross section (Phi delta(max)) of 5 is comparable to that the most efficient two-photon materials. This result provides a useful guideline to the design of efficient two-photon materials bearing pyrene as a pi-center.     

取代基对二噻吩并噻吩衍生物的双光子吸收性质的影响

利用ZINDO/SOS方法, 从理论上研究了对称和不对称取代两种情况下, 取代基对二噻吩并噻吩衍生物单双光子吸收性质的影响. 结果表明, 所设计的噻吩类分子具有较大的双光子吸收截面, 且双受体取代比双给体取代更有利于增大分子的双光子吸收截面. 同时发现, 此类分子受体取代可以显著增加波长较短的双光子峰附近的双光子吸收, 而给体取代则可以改善波长较长吸收峰附近的双光子吸收.