Bis(merocyanine) Hetero-Folda-Dimers: Evaluation of Exciton Coupling between Different Types of π-Stacked Chromphores

Exciton coupling between different types of chromophores has been rarely investigated. Herein, a systematic study on the exciton coupling between merocyanine chromophores of different conjugation length with varying excited state energies is presented. In this work well-defined hetero-dimer stacks were obtained upon folding of bis(merocyanine) dyes in nonpolar solvents. They show distinctly different absorption properties in comparison with the spectra of the single chromophores, revealing a significant coupling between the different chromophores. The simulated absorption spectra obtained from time-dependent density functional theory (TD-DFT) calculations are in good agreement with the experimental spectra. Our theoretical analysis based on an extension of Kasha's exciton theory discloses strong coupling between the dyes’ transition dipole moments despite of an excited-state energy difference of 0.60 eV between the chromophores.     

Orientation control of fluorescence resonance energy transfer using DNA as a helical scaffold

The efficiency of fluorescence resonance energy transfer (FRET) between two chromophores positioned at opposite ends of DNA base pair domains has been investigated. The base pair domain serves as a helical scaffold which defines both the distance between chromophores and the dihedral angle between their electronic transition dipole moments, each incremental base pair increasing the distance and stepping the dihedral angle. Fluorescence quantum yields and lifetimes have been determined for both the donor and acceptor chromophores. The experimental data are found to be in excellent accord with an oriented dipole model, rather than with the averaged dipole model conventionally assumed for FRET.     

Synthesis and characterization of indole-containing chromophores for second-order nonlinear optics

Push-pull indole-containing nonlinear optical chromophores with different acceptor and pi-conjugated moieties have been synthesized and characterized. Experimental measurements of the second-order nonlinear optical response demonstrated that the chromophores exhibit similar or superior optical nonlinearity compared with their analogues with an aniline moiety as the donor group, but the indole-based chromophores display blue-shifted absorption, even up to 30 nm.     

Dicyanomethylene-4H-pyran chromophores for OLED emitters, logic gates and optical chemosensors

Dicyanomethylene-4H-pyran (DCM) chromophores are typical donor-π-acceptor (D-π-A) type chromophores with a broad absorption band resulting from an ultra-fast internal charge-transfer (ICT) process. In 1989, Tang et al. firstly introduced a DCM derivative as a highly fluorescent dopant in organic electroluminescent diodes (OLEDs). Integration of ICT chromophore-receptor systems based on DCM chromophores with ion-induced shifts in absorption or emission is a convenient method to perform the logic expression for molecular logic gates. In recent years, various DCM-type derivatives have been explored due to their excellent optical-electronic properties and diverse structural modification. This feature article provides an insight into how the structural modification of DCM chromophores can be utilized for OLED emitters, logic gates and optical chemosensors. In addition, the aggregation-induced-emission (AIE) of DCM derivatives for further optical applications was also introduced.     

Catalytic Activity Towards Hydrogen Evolution Dependent of the Degree of Conjugation and Absorption of Six Organic Chromophores

Conjugated materials can, in many cases, absorb visible light because of their delocalized π electron system. Such materials have been widely used as a photoactive layers in organic photovoltaic devices and as photosensitizers in dye-sensitized solar cells. Additionally, these materials have been reported for applications in solar fuel production, working as photocatalysts for the hydrogen evolution reaction (HER). The synthesis of three flexible vinyl groups-containing chromophores is reported. The catalytic activity towards hydrogen evolution of these chromophores has been investigated and compared to their non-vinyl-containing analogues. The catalytic effect was confirmed using two different approaches: electrochemical, using the chromophores to modify a working electrode, and photocatalytic, using the chromophores combined with platinum nanoparticles. A relationship between the degree of conjugation and the catalytic activity of the chromophores has been observed with the electrochemical method, while a relationship between the UV absorption in the solid state and the photocatalytic effect with platinum nanoparticles was observed.     

H NMR investigation of the self-association of ethidium homodimer and its complexation with propidium iodide in aqueous solution

The self-association of a bis-intercalator, ethidium homodimer (EBH), and its hetero-association with phenanthridine dye, propidium iodide (PI), have been studied by 1D and 2D ¹H NMR spectroscopy using the analysis of proton chemical shifts changes in aqueous solution as a function of concentration and temperature. Experimental results have shown that dynamic equilibrium in solution includes different conformational states of EBH molecules: folded (F) and unfolded (U) forms, a dimer form (F₂) where an aromatic chromophore of one of EBH molecules is inserted (intercalated) between the linked chromophores of the other homodimer molecule and a trimer complex (F₃) with two partitially intercalated aromatic chromophores between the chromophores of the folded EBH molecule. It has been found that EBH associates with propidium iodide forming 1:1 complex, where PI is inserted between the chromophores of the folded form, and 1:2 complex resulting from intercalation of PI into F₂ EBH dimer. Thermodynamical parameters of EBH self-association and complexation between EBH and PI have been determined and conclusions about the nature of the physical forces responsible for the formation of intermolecular complexes have been made.     

Determination of the stereochemistry of condensation products between α,β-diamines and α,γ-dioxo compounds by circular dichroism, 1H NMR and x-ray diffraction

The absolute configuration of molecules containing two chromophores of the type -NH-CC-CO bridged by -?-?- have been studied in solution by UV absorption and circular dichroism. The spectra have been simulated by means of component curves shaped as skew gaussians. The data have been interpreted by means of exciton theory for coupled chromophores to give information about the relative orientation of the chromophores. The result is compared with the result of an X-ray structure determination of N,N'-bis(4-oxo-2-penten-2-yl)-R-1,2-diaminopropane.     

DNA molecular photonics

Synthetic DNA conjugates in which one or both ends of a short duplex is capped by a stilbene chromophore have been prepared and characterized crystallographically. Selective excitation of the chromophore can be used to initiate electron transfer processes in which a nucleobase serves as either an electron donor or an electron acceptor. These processes include hole- and electron injection and hole migration. The dynamics of these processes and its dependence on distance, driving force, and base sequence have been investigated by means of femtosecond time-resolved spectroscopy. Duplexes with identical chromophores at both ends have been used to study both the dynamics of electron transfer processes and exciton coupling between the two chromophores by means of circular dichroism spectroscopy. Duplexes with different chromophores can also be used to study distance dependence of both electron transfer and exciton coupling.     

Polyphenylene dendrimers with different fluorescent chromophores asymmetrically distributed at the periphery

A new synthetic approach leading to asymmetrically substituted polyphenylene dendrimers is presented. Following this method, polyphenylene dendrimers decorated with an increasing number of chromophores at the periphery have been obtained up to the second generation. Especially the synthesis of a polyphenylene dendrimer bearing three donor chromophores and one acceptor chromophore has been realized. Intramolecular energy transfer within this molecule is demonstrated by applying absorption and fluorescence measurements.     

An activated scheme for resonance energy transfer in conjugated materials

Energy transfer mechanism in conjugated materials has been demonstrated with an activated expression, which is equivalent to Fermi's golden rule. Spectral overlap integrals obtained from simulated spectra of model chromophores agree very well with the results obtained with the activated formula. Although this approach works best for chromophores with spectral profiles resembling a Gaussian distribution, the activated expression formula also performs quite well for chromophores with vibronically resolved spectra. Activation energies for exciton hopping can also be predicted using a phonon coupled exciton relaxation scheme. The accuracy of predictions with this new approach is quite attractive and hence should allow practical applications.     

Synthesis and Characterization of Dipolar Two-Photon Absorption Chromophores

It is a new interest to explore novel organic two-photon absorption (TPA) chromophores with large TPA cross section for their potential applications in various fields, such as three-dimensional optical data storage, micro- and nano-fabrication, biological imaging and optical limiting, and so on. As far as asymmetrical D-π-A type chromophores were concerned, larger TPA cross section can be obtained with the enhancement of electron-donation/electron-acception ability.[1] Recently, we have synthesized a series of new D-π-A type compounds. In these chromophores, stilbene or phenyl cyclo-bridged hexatriene is served as π-bridge, which terminated with a number of amino groups and dicyanomethylene unit (Scheme 1). All the chromophores can be obtained by the condensation reaction of aldehydes and active methyl or methenyl groups in good yields (72%～81%). The chromophores have been characterized by 1H NMR,IR, UV-vis, PL and EA. All these five chromophores in dilute solutions show strong red fluorescence (Table 1). The studies on the TPA properties are in progress.     

Synthesis and properties of glycidyl methacrylate copolymers with side chromophore groups

A number of styrylquinoline chromophores with carboxyl groups have been prepared through the interaction of 2-methylcinchonic acid with aromatic aldehydes of various chemical structures. The copolymer of glycidyl methacrylate and methyl methacrylate carrying side epoxide groups has been synthesized, and the chemical modification of the copolymer with the above chromophores has been performed. The thermal, spectral, and nonlinear optical properties of the chromophores and modified polymers have been studied.     

Reaction-based genetically encoded fluorescent hydrogen sulfide sensors

The detection of hydrogen sulfide (H(2)S), a toxic gas and an important biological signaling molecule, has been a long-time challenge. Here we report genetically encoded fluorescent protein (FP)-based probes that can selectively detect H(2)S. By expanding the genetic codes of E. coli and mammalian cells, FP chromophores were modified with the sulfide-reactive azide functional group. These structurally modified chromophores were selectively reduced by H(2)S, resulting in sensitive fluorescence enhancement detectable by spectroscopic and microscopic techniques. Exploration of a circularly permuted FP led to an improved sensor with faster responses, and the feasibility of using such a genetically encoded probe to monitor H(2)S in living mammalian cells has also been demonstrated.     

Three-branched dendritic dipolar nonlinear optical chromophores, more than three times a single-strand chromophore?

To elucidate the dependence of the nonlinear optical (NLO) response on the conformation of triply branched derivatives, a new series of D-pi-A dendrimers has been synthesized. A combined approach of experiments (UV-vis and EOA measurements) and computational predictions (semiempirical and ab initio) was applied both on the dendrimers and on the corresponding single-strand chromophores. It has been shown that depending on the surrounding media the NLO activity of a flexible dendrimer can be very different. Two limiting cases are proposed: (i) the dendrimer resembles a solution of the corresponding single-strand chromophores with about 3-fold concentration, where the hyperpolarizability is the sum of the effect of three noninteracting single-strand subunits ("independent chromophores" limit); (ii) the dendrimers show nearly parallel or helical alignments of the single-strand subunits. Because of this change of conformation the NLO activity can be enhanced up to nine times the value of the "independent chromophores" limit and, thus, are more than a single strand chromophore. Conformers of dendrimers with interacting single-strand chromophores have been identified experimentally in nonpolar solutions by the EOA spectroscopy and possible structures have been revealed by numerical calculations, which could moreover show the tendency of the effects on the hyperpolarizability due to structural changes of the flexible dendritic architecture. Implications for future research developments are given to implement the "more than three times" concept.     

Synthesis and second-order nonlinear optical properties of new chromophores containing benzimidazole, thiophene, and pyrrole heterocycles

A new series of thermally stable benzimidazole-based nonlinear optical (NLO) chromophores 4 and 5 have been developed. These chromophores possess a thienylpyrrolyl π-conjugated system attached to functionalized benzimidazole heterocycles. This feature leads to robust chromophores with excellent solvatochromic properties, high thermal stabilities and good molecular optical nonlinearities.     

Synthesis and two-photon absorption property of novel salen complexes incorporated with two pendant azo dyes

New salen compounds have been developed to possess two pendant azo dye chromophores. The two-photon absorption properties have been observed which result from the chromophores. The additive property has been found to exist as a result of no detrimental dipole-dipole interaction between chromophores.     

Chromophores from hexeneuronic acids: chemical behavior under peroxide bleaching conditions

Hexeneuronic acids (HexA) are a major cause of discoloration (yellowing/brightness reversion) in pulps from xylan-containing wood, being generated from the xylan’s 4-O-methylglucuronic acid residues. The HexA-derived chromophores, whose identification and structure confirmation have been described in the previous part of this series (Rosenau et al. in Cellulose, 2017), were subject to conditions of peroxide bleaching, i.e. treatment with hydrogen peroxide in alkaline medium. These chromophores, ladder-type oligomers of mixed aromatic-quinoid and mixed furanoid-benzoid character, are degraded relatively quickly to one major product, 2,5-dihydroxy-[1,4]-benzoquinone (DHBQ), and a minor component, 2,5-dihydroxyacetophenone (DHA). These two compounds, which have already been identified as two of the three key chromophores (besides 5,8-dihydroxy-[1,4]-naphthoquinone, DHNQ) in aged cellulosics, are potent chromophores themselves and are subsequently more slowly degraded to non-colored degradation products, according to pathways already described in previous parts of this series. The occurrence of DHBQ and DHA in the bleaching treatment of the HexA-derived chromophores establishes the link between HexA chemistry and the key chromophore classes of residual chromophores found in aged cellulosic materials.     

Effect of modified donor units on molecular hyperpolarizability of thienyl-vinylene nonlinear optical chromophores

Highly efficient and thermally stable nonlinear optical chromophores based on the phenyl vinylene thiophene vinylene (FTC) donor-π-acceptor structure have been synthesized and investigated. The donor part of the chromophores was modified with additional donor units, resulting in the enhanced nonlinear optical property with large molecular hyperpolarizability. Hyper-Rayleigh scattering measurement indicated nearly threefold increase of the molecular hyperpolarizability for novel chromophores compared with the benchmark FTC chromophore. Furthermore, measurement of the electro-optic coefficient confirmed that enhancement of microscopic molecular hyperpolarizability of the chromophores can be effectively translated into macroscopic electro-optic property. Measured electro-optic coefficients were nearly twofold larger than that for the benchmark FTC. Thermal analysis indicated that the synthesized chromophores showed the excellent temperature stability with decomposition temperatures up to 280 °C.     

Organization and orientation of amphiphilic push-pull chromophores deposited in Langmuir-Blodgett monolayers studied by second harmonic generation and atomic force microscopy

Orientation and organization of two amphiphilic push-pull chromophores mixed with two phospholipids (dipalmitoylphosphatidylcholine and dioleoylphosphatidylcholine) in Langmuir-Blodgett (LB) monolayers are investigated by second harmonic generation. The LB monolayers have also been characterized by atomic force microscopy and UV-vis spectroscopy. The effective molecular orientations and hyperpolarizabilities of the chromophores are studied as a function of the phospholipid concentrations. The experimental results are discussed within the frame of a model of orientational distribution of the chromophores which gives the orientational mean angle and bounds on the orientational disorder. The mean orientation of the chromophores is found to be within 45-55 degrees whereas their hyperpolarizability coefficients, measured with respect to quartz, are estimated to be in the range (0.3-0.7) x 10(-27) esu taking account of the maximal orientational disorder.     

Strong two photon absorption and photophysical properties of symmetrical chromophores with electron accepting edge substituents

Two photon absorption (TPA) and photophysical properties of three new symmetrical chromophores with electron accepting phthalimide edge substituents have been studied. The three chromophores contain fluorene, alcoxy-substituted divinyl benzene, and carbazole moieties as central cores, respectively. The femtosecond time-resolved fluorescence upconversion spectroscopy and two photon excited fluorescence technique have been carried out. The effect of solvent polarity on TPA and on photophysics has also been determined. Ultrafast fluorescence dynamics, with decay times ranging from 1 to 13 ps, are revealed in polar solvents. This is attributed to the relaxation of the chromophores to the intramolecular charge transfer state. The chromophore bearing fluorene central core, being of the type A-pi-A, is the most efficient concerning TPA. Strong TPA, with a cross section value as high as 2100 GM at an excitation wavelength of 770 nm is found in acetophenone which is a solvent of intermediate polarity. The TPA spectra were also reproduced using a sum over states three-state model. A study of the TPA induced photobleaching of the fluorene molecule, doped in a solid poly(methyl-methacrylate) film, has shown that this material is very promising for efficient TPA optical data storage.