Leszek Mateusz Mazur

Electronic energy and electron transfer processes in photoexcited donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units.

We investigate the photophysical properties of organic donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units linked by a non-conjugated flexible bridge in solution using complementary optical spectroscopy techniques. When these molecules are diluted in dichloromethane solution, energy transfer from the triphenylene to the perylene diimide excited moieties is evidenced by time-resolved fluorescence measurements resulting in a quenching of the emission from the triphenylene moieties. Simultaneously, another quenching process that affects the emission from both donor and acceptor units is observed. Solution ultrafast transient absorption measurements provide evidence of photo-induced charge transfer from either the donor or the acceptor depending upon the excitation. Overall, the analysis of the detailed time-resolved spectroscopic measurements carried out in the dyad and triad systems as well as in the triphenylene and perylene diimide units alone provides useful information both to better understand the relations between energy and charge transfer processes with molecular structures, and for the design of future functional dyad and triad architectures based on donor and acceptor moieties for organic optoelectronic applications.

π-Expanded 1,3-diketones – synthesis, optical properties and application in two-photon polymerization

Four π-expanded α,β-unsaturated 1,3-diketones have been prepared via attaching strong electron-donating and electron-withdrawing groups at positions 9 and 10 of the anthracene scaffold. The strategic incorporation of (C12H25)2N groups at the periphery of these D–π–A molecules resulted in dyes with excellent solubility in most organic solvents. These non-planar diketones possess very broad absorption of light and negligible fluorescence. The two-photon absorption cross-section was measured via Z-scan as well as by two-photon excited fluorescence. The results clearly confirm that, in the case of compounds possessing such small fluorescence quantum yields, the Z-scan was a more reliable approach. Depending on the chemical structure, these compounds exhibited two-photon absorption cross-sections (σ2) up to 2500 GM at 725 nm. For the first time an α,β-unsaturated ketone derived from a proton sponge has been synthesized and was shown to possess optical features distinct from its simpler analogs, such as weak emission. All studied ketones possessed two-photon absorption cross-sections ∼200 GM at wavelength of two-photon polymerization (i.e. 800 nm) and broad fabrication windows have been achieved using all these dyes as photoinitiators.

2,5-Bis(azulenyl)pyrrolo[3,2-b]pyrroles – the key influence of the linkage position on the linear and nonlinear optical properties

The first route towards pyrrolo[3,2-b]pyrroles containing two azulene moieties at positions 2 and 5 was developed. The key step of this approach is the three-step transformation of pyridine scaffolds into azulene via sequential N-arylation followed by ring-opening and a reaction with cyclopentadiene. The resulting quadrupolar acceptor–donor–acceptor compounds possess interesting optical properties such as bathochromically shifted absorption with the magnitude of the red-shift strongly dependent on the linkage position. Two-photon absorption of these functional dyes is markedly different from that of previously described pyrrolo[3,2-b]pyrroles. The experimental optical spectra were rationalized using time-dependent density functional theory calculations of both the linear and nonlinear optical properties.

Nonlinear absorption and nonlinear refraction: maximizing the merit factors

Both nonlinear absorption and nonlinear refraction are effects that are potentially useful for a plethora of applications in photonics, nanophotonics and biophotonics. Despite substantial attention given to these phenomena by researchers studying the merits of disparate systems such as organic materials, hybrid materials, metal-containing molecules and nanostructures, it is virtually impossible to compare the results obtained on different materials when varying parameters of the light beams and different techniques are employed. We have attempted to address the problem by studying the properties of various systems in a systematic way, within a wide range of wavelengths, and including the regions of onephoton, two-photon and three-photon absorption. The objects of our studies have been typical nonlinear chromophores, such as π-conjugated molecules, oligomers and polymers, organometallics and coordination complexes containing transition metals, organometallic dendrimers, small metal-containing clusters, and nanoparticles of various kinds, including semiconductor quantum dots, plasmonic particles and rare-earth doped nanocrystals. We discuss herein procedures to quantify the nonlinear response of all of these systems, by defining and comparing the merit factors relevant for various applications.

Specific Recognition of G-Quadruplexes Over Duplex-DNA by a Macromolecular NIR Two-Photon Fluorescent Probe

The implication of guanine-rich DNA sequences in biologically important roles such as telomerase dysfunction and the regulation of gene expression has prompted the search for structure-specific G-quadruplex agents for targeted diagnostic and therapeutic applications. Herein, we report on a near-infrared (NIR) two-photon poly(cationic) anthracene-based macromolecule able to selectively target G-quadruplexes (G4s) over genomic double-stranded DNA. In particular, the striking changes in its linear and third-order nonlinear optical properties, combined with the emergence of a strong induced electronic circular dichroism (ECD) signal upon binding to canonical and noncanonical DNA secondary structures allowed for a highly specific detection of several different G4s. Furthermore, through a detailed computational analysis we bring compelling evidence that our probe intercalation within G4s is a thermodynamically favored event, and we fully rationalize the spectroscopic evolution resulting from this complexation event by providing a reasonable explanation regarding the origin of the peculiar ECD effect that accompanies it.

Two-Photon Macromolecular Probe Based on a Quadrupolar Anthracenyl Scaffold for Sensitive Recognition of Serum Proteins under Simulated Physiological Conditions

The binding interaction of a biocompatible water-soluble polycationic two-photon fluorophore (Ant-PIm) toward human serum albumin (HSA) was thoroughly investigated under simulated physiological conditions using a combination of steady-state, time-resolved, and two-photon excited fluorescence techniques. The emission properties of both Ant-PIm and the fluorescent amino acid residues in HSA undergo remarkable changes upon complexation allowing the thermodynamic profile associated with Ant-PIm–HSA complexation to be accurately established. The marked increase in Ant-PIm fluorescence intensity and quantum yield in the proteinous environment seems to be the outcome of the attenuation of radiationless decay pathways resulting from motional restriction imposed on the fluorophore. Fluorescence resonance energy transfer and site-marker competitive experiments provide conclusive evidence that the binding of Ant-PIm preferentially occurs within the subdomain IIA. The pronounced hypsochromic effect and increased fluorescence enhancement upon association with HSA, compared to that of bovine serum albumin (BSA) and other biological interferents, makes the polymeric Ant-PIm probe a valuable sensing agent in rather complex biological environments, allowing facile discrimination between the closely related HSA and BSA. Furthermore, the strong two-photon absorption (TPA) with a maximum located at 820 nm along with a TPA cross section σ2 > 800 GM, and the marked changes in the position and intensity of the band upon complexation definitely make Ant-PIm a promising probe for two-photon excited fluorescence-based discrimination of HSA from BSA.

Structure–charge transfer property relationship in self-assembled discotic liquid-crystalline donor–acceptor dyad and triad thin films

The photophysical properties of donor–acceptor (D–A) and donor–acceptor–donor (D–A–D) liquid crystalline dyads and triads based on two different discotic mesogens are examined in thin films by steady-state optical spectroscopy and subpicosecond transient absorption measurements. In these systems, triphenylene and perylene bisimide units are covalently linked by flexible decyloxy chain(s) and act as an electron donor (D) and acceptor (A), respectively. These discotic liquid-crystalline systems form well-separated D and A π-stacked columnar structures in thin films. The absorption spectra of the films indicate an aggregation of the perylene bisimide and triphenylene moieties along the columns. Steady-state photoluminescence measurements show a strong fluorescence quenching that is mainly attributed to a photo-induced charge transfer process taking place between the triphenylene and perylene bisimide units. Subpicosecond transient absorption measurements show that the photoinduced charge transfer (CT) states in the dyad and triad films are formed within 0.3 ps and recombine on a 150–360 ps time scale. In addition, a correlation between the dynamics of the charge recombination process and the spacing distances between D and A units can be established in the dyad and triad films. This study provides important information on the relationship between molecular packing and the charge transfer properties in such self-organized D and A columnar nanostructures.

Application of Negative Curvature Hollow-Core Fiber in an Optical Fiber Sensor Setup for Multiphoton Spectroscopy

In this paper, an application of negative curvature hollow core fiber (NCHCF) in an all-fiber, multiphoton fluorescence sensor setup is presented. The dispersion parameter (D) of this fiber does not exceed the value of 5 ps/nm × km across the optical spectrum of (680–750) nm, making it well suited for the purpose of multiphoton excitation of biological fluorophores. Employing 1.5 m of this fiber in a simple, all-fiber sensor setup allows us to perform multiphoton experiments without any dispersion compensation methods. Multiphoton excitation of nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) with this fiber shows a 6- and 9-fold increase, respectively, in the total fluorescence signal collected when compared with the commercial solution in the form of a hollow-core photonic band gap fiber (HCPBF). To the author’s best knowledge, this is the first time an NCHCF was used in an optical-fiber sensor setup for multiphoton fluorescence experiments.

Two- and three-photon absorption properties of fan-shaped dendrons derived from 2,3,8-trifunctionalized indenoquinoxaline units: synthesis and characterization

A model compound set that contains a series of fan-shaped chromophores using 2,3,8-trifunctionalized indenoquinoxaline units as the major building block of their π-framework was synthesized and characterized for their two- and three-photon absorption properties in the femtosecond regime based on two-photon-excited fluorescence and Z-scan techniques. The experimental results show that these dendritic fluorophores manifest strong and wide-dispersed two- and three-photon absorption bands within the near-infrared region, which indicates that 2,3,8-trifunctionalized indenoquinoxaline units are favorable building moieties for the construction of highly active multi-photon dyes. The maximum values of two- and three-photon absorption cross-sections for the largest dendron (i.e. compound D4) are ≈24 800 GM and 6 × 10−78 cm6 s2, respectively. A nearly linear ascending relationship between π-structural expansion and nonlinear absorption is observed for these compounds, implying that the currently utilized structural arrangement does not exert deleterious or cooperative effects on the multi-photon absorption properties of this model system. In addition, a representative dendritic structure is selected to demonstrate efficient optical power-limiting against femtosecond laser pulses at 790 nm.