Two-photon Absorption Properties Research Articles

Silafluorene as a promising core for cell-permeant, highly bright and two-photon excitable fluorescent probes for live-cell imaging

In this study, we report the synthesis, linear and non-linear photophysical studies and live-cell imaging of two two-photon activatable probes based on a silafluorene core: SiFluo-V and SiFluo-L. Thanks to their quadrupolar (A-π-D-π-A) design, these probes exhibit respectively good to impressive two-photon cross-sections (from 210 GM to 2150 GM). TD-DFT calculations support the experimental evidence that SiFluo-L displays far better two-photon absorption properties than SiFluo-V. Moreover, SiFluo-L possesses all requirements for bioimaging as it is water soluble, cell-permeant and presents a low cytotoxicity (IC80 ≥ 10 μM). It labels mitochondria in live-cell imaging at low laser power with high brightness, contrast and photostability. This study demonstrates that silafluorene is a promising core to develop new two-photon fluorophores for live-cell imaging.

Water Triggered Synthesis of Highly Stable and Biocompatible 1D Nanowire, 2D Nanoplatelet, and 3D Nanocube CsPbBr3 Perovskites for Multicolor Two-Photon Cell Imaging.

Two-photon imaging in the near-infrared window holds huge promise for real life biological imaging due to the increased penetration depth. All-inorganic CsPbX3 nanocrystals with bright luminescence and broad spectral tunability are excellent smart probes for two-photon bioimaging. But, the poor stability in water is a well-documented issue for limiting their practical use. Herein, we present the development of specific antibody attached water-resistant one-dimensional (1D) CsPbBr3 nanowires, two-dimensional (2D) CsPbBr3 nanoplatelets, and three-dimensional (3D) CsPbBr3 nanocubes which can be used for selective and simultaneous two-photon imaging of heterogeneous breast cancer cells in the near IR biological window. The current manuscript reports the design of excellent photoluminescence quantum yield (PLQY), biocompatible and photostable 1D CsPbBr3 nanowires, 2D CsPbBr3 nanoplatelets, and 3D CsPbBr3 nanocubes through an interfacial conversion from zero-dimensional (0D) Cs4PbBr6 nanocrystals via a water triggered strategy. Reported data show that just by varying the amount of water, one can control the dimension of CsPbBr3 perovskite crystals. Time-dependent transition electron microscopy and emission spectra have been reported to find the possible pathway for the formation of 1D, 2D, and 3D CsPbBr3 nanocrystals from 0D Cs4PbBr6 nanocrystals. Biocompatible 1D, 2D, and 3D CsPbBr3 nanocrystals were developed by coating with amine–poly(ethylene glycol)–propionic acid. Experimental data show the water-driven design of 1D, 2D, and 3D CsPbBr3 nanocrystals exhibits strong single-photon PLQY of ∼66–88% as well as excellent two-photon absorption properties (σ2) of ∼8.3 × 105–7.1 × 104 GM. Furthermore, reported data show more than 86% of PL intensity remains for 1D, 2D, and 3D CsPbBr3 nanocrystals after 35 days under water, and they exhibit excellent photostability of keeping 99% PL intensity after 3 h under UV light. The current report demonstrates for the first time that antibody attached 1D and 2D perovskites have capability for simultaneous two-photon imaging of triple negative breast cancer cells and human epidermal growth factor receptor 2 positive breast cancer cells. CsPbBr3 nanocrystals exhibit very high two-photon absorption cross-section and good photostability in water, which are superior to those of commonly used organic probes (σ2 = 11 GM for fluorescein), and therefore, they have capability to be a better probe for bioimaging applications.

Enhanced optical power limiting and visible luminescence in colloidal dispersion of ultra-small Au nanoclusters synthesized by single-pot chemical technique

Here, we present a detailed investigation on the synthesis and nonlinear multiphoton absorption properties of the colloidal solution of Au nanoclusters (AuNCs) which contains the atomic clusters, with the number of atoms per cluster (NAC) of only one (Au1NC) and two (Au2NC). These AuNCs are synthesized by an easy single step one-pot simple chemical process and by using dimethylformamide (DMF) both as reducer and stabilizer. The presence of both Au1NC and Au2NC are found in the sample by their distinct signature in the UV–Vis. absorption spectrum as well as in the high-resolution mass spectrum. The synthesized material has been found to exhibits a strong and stable blue-luminescence with a moderately high quantum yield (QY) of 12.4% when excited with UV light. The nonlinear optical two-photon absorption (2PA) properties of Au1, Au2NC solutions are being reported here by Z-scan studies, for the first time, by using both 10 ns and 100 fs pulse laser radiations having wavelength of 532 nm. It is significantly noted here that the synthesized AuNCs are found to exhibit reverse saturable absorption (RSA) when excited either by ns or by fs laser pulses. A high third-order nonlinear susceptibility (ꭓ(3)) of the order of 10−13 (esu) of the synthesized materials are obtained under fs laser excitation and it is attributed to the 2PA through electronic band to band transition. In contrast, the variation of the 2PA coefficient (β) with input intensity (I0) represents the footprint of free carrier involvement in the enhanced nonlinear absorption in the case of ns excitation. Furthermore, through the non-saturable nonlinear multiphoton absorption, the synthesized AuNCs exhibit excellent optical power limiting phenomenon with the limiting threshold (Fth) of 9.1 mJ/cm2 (fs excitation) and 2.02 J/cm2 (ns excitation) owing to their enhanced 2PA coefficient. Therefore, we believe that our synthesized ultra-small colloidal AuNCs can be used as the promising candidate material for advanced photonics application in the future.

Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging.

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP)n (n=1-3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40-0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δTPA values of TAT-(ZnP)2 and TAT-(ZnP)3 further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D-π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D-π-A-D multipolar array.

Novel yellow- to red-emitting fluorophores: Facile synthesis, aggregation-induced emission, two-photon absorption properties, and application in living cell imaging

Four novel yellow-to red-emitting fluorophores with a 1-(2-hydroxyethyl) pyridinium core and different electron-donating terminal moieties (N-methylcarbazole, N,N-dibutylbenzenamine, N-methylpyrrole, and 2-methylfuran) were designed and facilely synthesized via the one-step Knoevenagel condensation. All these compounds (HPs) were characterized by 1H NMR, 13C NMR, and HRMS. Their photophysical properties including linear absorption, one-photon excited fluorescence, two-photon absorption, and two-photon excited fluorescence, were systematically investigated in various solvents. And the density functional theory calculations were conducted to analyze the electronic structures of HPs. The two-photon absorption cross-sections (δ) values of HPs measured by the Z-scan technique were determined to be as large as 1354 (1HP-CZ), 4462 (2HP-BA), 836 (3HP-PR), and 2944 GM (4HP-FU) in DMSO. The two-photon action cross-sections (Φ × δ) values of 1HP-CZ and 2HP-BA in H2O measured by the two-photon induced fluorescence method were about 50 GM. 1HP-CZ, 3HP-PR, and 4HP-FU also exhibited good water solubility. Meanwhile, it was found that 2HP-BA exhibited notable aggregation-induced emission characteristic in DMSO/H2O mixture. The aggregate particle size distribution of 2HP-BA was measured by the dynamic light scattering method, and the aggregation characteristic of 2HP-BA was observed by the transmission electron microscopy. Besides, 2HP-BA also exhibited red emission. Then, HPs with relatively low cytotoxicity were used for one- and two-photon excited fluorescence imaging in living HepG2 cells. The results indicate that HPs are potential candidates in the bioimaging field due to their photophysical properties and biocompatibility.

Two-Photon Initiating Efficiency of a Ditopic Alkoxynitrostilbene Reacting through a Self-Regenerative Mechanism.

The photophysical properties and the photoinitiating reactivity of a ditopic alkoxynitrostilbene were compared to those of its single branch chromophore used as a reference. Whereas a trivial additive effect is observed when considering the one- and two-photon absorption properties, a clear and very significant amplification has been highlighted for the photoreactivity of this free radical photoinitiator which was used as a hydrogen abstractor in presence of an aliphatic amine co-reactant. We indeed demonstrate that the proximity of two nitroaromatics moieties within the same molecular architecture gives rise to an original cycling mechanism based on a stepwise photo triggering of each photoredox center followed by a subsequent regenerative process. The combination of a high two-photon absorption cross-section (δ780nm ≈330 GM) with a strong enhancement in photoreactivity makes this nitrostilbene bichromophore a very suitable candidate for two-photon polymerization applications.

Aggregation-Enhanced Two-Photon Absorption of Anionic Conjugated Polyelectrolytes.

The two-photon absorption properties of anionic poly(phenylene ethynylene)-type conjugated oligo- and polyelectrolytes are studied in molecularly dissolved and aggregated forms in aqueous solution. Several different polyvalent cations are used to induce aggregation. It is found that both materials in the aggregated form exhibit enhanced two-photon excited fluorescence (2PEF) and two-photon cross section (σ2) compared with the molecularly dissolved structures. The 2PEF and σ2 are unaffected by the nature of the polyvalent cation that is used to induce aggregation. The two-photon absorption cross section enhancement arises because of the increase in the difference dipole moment (Δμ) in the aggregates of the conjugated materials, an effect that is attributed to the introduction of charge transfer character into the aggregate excited state.

Enhancement of one- and two-photon absorption and visualization of intramolecular charge transfer of pyrenyl-contained derivatives.

To further improve the pyrenyl-contained derivatives two-photon absorption (TPA) and third-order nonlinear optical (NLO) properties, three steps of optimization are employed based on experimental molecule PCVS-B: heteroatomic substitution, exchanging the position of double bonds and adding a branch. The contributions of π electrons to localized orbital locators and Mayer bond orders (LOL-π and IABπ) show that the second step can enhance the chemical interaction between pyrenyl and the branched-chain. Two visual methods of charge density difference (CDD) and transition density matrix (TDM) are combined to intuitively analyze the intramolecular charge transfer (ICT) process of one (two) photon absorption; results show that both following two steps can increase the degree of ICT on the conjugated plane of the pyrenyl. The sum over state (SOS) model was used to find out the dominant two-photon transition process. The difference between the dipole moments obtained by the McRae equation is applied to the three-state model, revealing the inherent law of the second static hyperpolarizability.

A pyrene-based two-photon excitable fluorescent probe to visualize nuclei in live cells.

The two-photon absorption properties of a pyrene-pyridinium dye (1) were studied for potential application in two-photon spectroscopy. When probe 1 was used in cellular two-photon fluorescence microscopy imaging, it allowed the visualization of nuclei in live cells with a relatively low probe concentration (such as 1 μM). Spectroscopic evidence further revealed that probe 1 interacted with DNA as an intercalator. The proposed DNA intercalation properties of probe 1 were consistent with the experimental findings that suggested that the observed nucleus staining ability is dependent on the substituents on the pyridinium fragment of the probe.

12]aneN3-Based Gemini-Type Amphiphiles with Two-Photon Absorption Properties for Enhanced Nonviral Gene Delivery and Bioimaging.

Although a plethora of nonviral gene vectors have been developed for potential gene therapy, imageable gemini surfactants with stimuli-responsiveness and high transfection efficiency are still scarce for gene delivery. Herein, three gemini amphiphiles (DEDPP-4/8/12) consisting of an aggregation-induced emission (AIE) central fluorophore: 5,6-diphenylpyrazine-2,3-diester (DEDPP), decorated with triazole-[12]aneN3 as the hydrophilic moiety and alkyl chains of various lengths as the hydrophobic moiety, were designed and synthesized for trackable gene delivery via optical imaging. All three amphiphiles exhibited ultralow critical micelle concentrations (CMCs) (up to 3.40 × 10-6 M), prominent two-photon absorption properties, and solvatochromic fluorescence. Gel electrophoresis assays demonstrated that the migration of plasmid DNA was completely retarded after condensation with these gemini amphiphiles at low concentrations (up to 10 μM). In addition, the ester bond in these amphiphiles may facilitate vector degradation and DNA release, in response to esterase and the acidic environment inside cells. Upon self-assembly with DOPE to form liposomes, DEDPP-8/DOPE achieved the best transfection efficiency in four cell lines, and the transfection efficiency of DEDPP-8/DOPE in HeLa cell lines was 23.5-fold higher than that of Lipo2000, which is unusually high for small organic molecule-based nonviral vectors. Furthermore, excellent transfection efficiency of DEDPP-8/DOPE was obtained in the presence of serum, and the red fluorescence protein (RFP) gene was successfully transfected in zebrafish embryos. Both one- and two-photon fluorescence imaging clearly demonstrated the delivery process of plasmid DNA. This study demonstrated that gemini-type amphiphiles composed of a two-photon fluorophore core conjugated with triazole-[12]aneN3 via an ester bond afforded an unprecedentedly high transfection efficiency with excellent biocompatibility, which may provide new insights for the design and development of multifunctional nonviral gene vectors for imageable gene delivery.

Multiscale Modeling of Two-Photon Probes for Parkinson's Diagnostics Based on Monoamine Oxidase B Biomarker.

Monoamine oxidase B (MAO-B) is a potential biomarker for Parkinson’s disease (PD), a neurodegenerative disease associated with the loss of motor activities in human subjects. The disease state is associated with dopamine deprival, and so the inhibitors of MAO-B can serve as therapeutic drugs for PD. Since the expression level of MAO-B directly correlates to the disease progress, the distribution and population of this enzyme can be employed to monitor disease development. One of the approaches available for estimating the population is two-photon imaging. The ligands used for two-photon imaging should have high binding affinity and binding specificity toward MAO-B along with significant two-photon absorption cross sections when they are bound to the target. In this article, we study using a multiscale modeling approach, the binding affinity and spectroscopic properties (one- and two-photon absorption) of three (Flu1, Flu2, Flu3) of the currently available probes for monitoring the MAO-B level. We report that the binding affinity of the probes can be explained using the molecular size and binding cavity volume. The experimentally determined one-photon absorption spectrum is well reproduced by the employed QM/MM approaches, and the most accurate spectral shifts, on passing from one probe to another, are obtained at the coupled-cluster (CC2) level of theory. An important conclusion from this study is also the demonstration that intrinsic molecular two-photon absorption strengths (δ2PA) increase in the order δ2PA (Flu1) > δ2PA (Flu2) > δ2PA (Flu3). This is in contrast with experimental data, which predict similar values of two-photon absorption cross sections for Flu1 and Flu3. We demontrate, based on the results of electronic-structure calculations for Flu1 that this discrepancy cannot be explained by an explicit account for neighboring residues (which could lead to charge transfer between a probe and neighboring aromatic amino acids thus boosting δ2PA). In summary, we show that the employed multiscale approach not only can optimize two-photon absorption properties and verify binding affinity, but it can also help in detailed analyses of experimental data.

Two-Photon Antenna Sensitization of Curium: Evidencing Metal-Driven Effects on Absorption Cross Section in f-Element Complexes.

Two-photon-excited fluorescence spectroscopy is a powerful tool to study the structural and electronic properties of optically active complexes and molecules. Although numerous lanthanide complexes have been characterized by two-photon-excited fluorescence in solution, this report is the first to apply such a technique to actinide compounds. Contrasting with previous observations in lanthanides, we demonstrate that the two-photon absorption properties of the complexes significantly depend on the metal (4f vs 5f), with Cm(III) complexes showing significantly higher two-photon absorption cross sections than lanthanide analogues and up to 200-fold stronger emission intensities. These results are consistent with electronic and structural differences between the lanthanide and actinide systems studied. Hence, the described methodology can provide valuable insights into the interactions between f-elements and ligands, along with promising prospects on the characterization of scarce compounds.

Responsive mechanism and coordination mode effect of a bipyridine-based two-photon fluorescent probe for zinc ion**Project supported by the Natural Science Foundation of Shandong Province, China (Grant No. ZR2014AM026).

The properties of one-photon absorption (OPA), emission and two-photon absorption (TPA) of a bipyridine-based zinc ion probe are investigated employing the density functional theory in combination with response functions. The responsive mechanism and coordination mode effect are explored. The structural fluctuation is illustrated by molecular dynamics simulation. The calculated OPA and emission wavelengths of the probe are consistent with the experimental data. It is found that the red-shift of OPA wavelength and the enhancement of TPA intensity are induced by the increased intra-molecular charge transfer mechanism upon metal binding. The structural fluctuation could result in the blue-shift of TPA wavelength and the decrease of the TPA cross section. The TPA properties are quite different among the zinc complexes with different coordination modes. The TPA wavelength of the complexes with two ligands is close to that of the probe, which is in agreement with the experimental observation.

Postsynthetic Framework Contraction Enhances the Two-Photon Absorption Properties of Pillar-Layered Metal–Organic Frameworks

Aggregation-induced emission (AIE) dyes have been shown to be a potential ligand class for multiphoton absorbing metal–organic frameworks (MPA-MOFs); however, the influence of framework flexibility on the local ligand conformation and its ramifications on the nonlinear absorption properties of this material class have sparsely been understood. In this study, we systematically investigate the two-photon absorption properties of two pillar-layered MOFs comprising tetraphenylethylene AIE ligands and compare the results to the organic ligand in crystal form, using a combination of linear and nonlinear optical characterization methods and electronic-structure calculations. We demonstrate that self-confining the AIE ligand is key to enhance the nonlinear optical absorption properties, as a structure transformation to contracted frameworks strongly increases the two-photon absorption response, which can be addressed by specific ligand substitution. Our results have important implications on the design of MPA-MOFs and provide synthetic guidelines not only from a fundamental point of view but also application-wise.

Acetylene bridged D-(π-A)2 type dyes containing benzophenone moieties: Photophysical properties, and the potential application as photoinitiators

Acetylene bridged acceptor-π-bridge-donor-π-bridge-acceptor (A-π-D-π-A) dyes (DBPs) based on benzophenone were designed and synthesized via Sonogashira coupling reaction utilizing carbazole/phenothiazine/triphenylamine as electron donating groups. The photophysical properties, photochemistry characteristics, as well as the two-photon absorption properties were studied. All dyes exhibited excellent intra-/intermolecular charge transfer properties upon excitation, and large two photon absorption cross sections in the wavelength range of 720~860 nm. Significant differences in fluorescence and photochemistry properties were found depending on the electron donating groups. The rigid carbazole favored hybridization of benzophenone like local excited state and intramolecular charge transfer excited state, which resulted in abnormal changes in fluorescence quantum yield, poor photostability, and good initiating ability both as Norrish Ⅱ initiator and as sensitizer for iodonium salt. However, the butterfly-shaped phenothiazine and propeller-shaped triphenylamine facilitated intramolecular charge transfer excited states, which resulted in typical positive solvatochromism effect, good photostabilities, and lacking of initiating ability as Norrish Ⅱ initiator.

Highly Conjugated, Fused-Ring, Quadrupolar Organic Chromophores with Large Two-Photon Absorption Cross-Sections in the Near-Infrared.

The two-photon absorption (2PA) properties are investigated for two series of organic, π-conjugated, fused-ring, quadrupolar A-π-D-π-A chromophores of the type originally developed as nonfullerene acceptors for organic photovoltaics. These molecules are found to exhibit large nondegenerate two-photon absorption (ND2PA) cross-sections (ca. 6-27 × 103 GM) in the near-infrared (NIR). In the first series, involving molecules of varying core size, ND2PA spectra and cross-sections characterized by femtosecond ND2PA spectroscopy in chloroform solutions reveal that increases in core size, and thus conjugation length, leads to substantially red-shifted and enhanced 2PA. In a second series, variation of the strength of the terminal acceptor (A) with constant core size (seven rings, indacene-based) led to less dramatic variation in the 2PA properties. Among the two core types studied, compounds in which the donor has a thieno[3,2-b]thiophene center demonstrate larger 2PA cross-sections than their indacene-centered counterparts, due to the greater electron-richness of their cores amplifying intramolecular charge transfer. Excited-state absorption (ESA) contributions to nonlinear absorption measured by open-aperture Z-scans are deduced for some of the compounds by analyzing the spectral overlap between 2PA bands and NIR ESA transitions obtained by ND2PA and transient absorption measurements, respectively. ESA cross-sections extracted from transient absorption and irradiance-dependent open-aperture Z-scans are in reasonable agreement, and their moderate magnitudes (ca. 10-21 m2) suggest that, although ESA contributions are non-negligible, the effective response is predominantly instantaneous 2PA.

Facile synthesis and exploration of excited state assisted two-photon absorption properties of D-A-D type thiophene-pyridine derivatives.

A series of trigonal-shaped molecules (TPyT and TPyP) and a polymer (P2TPy) with donor-acceptor-donor (D-A-D) structural arrangement were designed with thiophene and 2,4,6-trisubstituted pyridine as the backbone i.e., a 4-(4-(decyloxy)phenyl)-2,6-di(thiophen-2-yl)pyridine core structure, for the first time and synthesized via a microwave assisted one pot reaction. The extension of conjugation of the system by substituting thiophene acrylonitrile (TPyT) and phenyl acrylonitriles (TPyP and P2TPy) via low cost condensation reactions improved the linear optical, electronic and thermal properties of the synthesized compounds. Furthermore, the nonlinear absorption (NLA) was also enriched appreciably by increasing the conjugation. The three compounds showed an "effective two-photon absorption" phenomenon with the NLA coefficient (βeff) of the order of 10-10 m W-1. The suitability to be utilized in the fabrication of all-optical limiting devices is best achieved by polymer P2TPy as it exhibits substantially higher βeff (7.02 × 10-10 m W-1) and an extremely low optical limiting threshold (1.42 J cm-2).

The theory of cysteine two-photon fluorescence probes of coumarinocoumarin derivatives and kinetics of ICT and PET mechanisms of probe molecules

Cysteine is an essential amino acid in the synthesis of human protein. Therefore, the effective detection of cysteine in living organisms is of great significance. In this paper, first-principles are used to systematically study the fluorescence recognition mechanism and two-photon absorption properties of a series of novel two-photon (TP) fluorescent probes for cysteine. These probes are constructed based on coumarinocoumarin derivatives possessing the excellent fluorescence properties of coumarin molecules and the experimental fact that sporadic coumarinocoumarin can be used as a fluorescent probe, the recognition of which depends on enabled photo-induced electron transfer (PET) and intramolecular charge transfer (ICT) mechanisms toward cysteine. The results show that the transition dipole moments of coumarinocoumarin and monomer coumarin are significantly different, which allows the coumarinocoumarin to break the limit of the linear increase in the dipole moment vector of the monomer coumarin in the direction and magnitude. The magnitude of the two-photon cross-section value (δmaxT) depends on the state dipole moment (μjj (μii)) of the transition channel and the transition dipole moment (μij) of the coherent channel. Through the above research, we propose that (1) the length of the π conjugated chain can be increased along the 7-site of the coumarinocoumarin skeleton; (2) extend the π conjugated chain along different paths to change the state dipole moment of the transition channel of the target molecule and the direction of the transition dipole moment vector of the coherent channel to improve the TPA cross-section values of the probe molecule. Moreover, maximum TPA can be achieved in the range of 700–1000 nm for designed probe molecules, effectively avoiding factors such as the self-fluorescence of biological tissues and background interference. CCy-1-OH ∼ CCy-3-OH and CCy-7-OH molecules are designed to be excellent candidates for TP fluorescent probes. We hope the study can provide useful theoretical basis for cysteine imaging research.

Simple Perylene Diimide Cyclohexane Derivative With Combined CPL and TPA Properties.

In this work we describe the linear and non-linear (chiro)optical properties of an enantiopure bis-perylenediimide (PDI) cyclohexane derivative. This compound exhibits upconversion based on a two-photon absorption (TPA) process with a cross-section value of 70 GM together with emission of circularly polarized luminescence (CPL), showing a glum in the range of 10−3. This simple structure represents one of the scarce examples of purely organic compounds combining both TPA and CPL responses, together with large values of molar absorptivity and fluorescence quantum yield with emission in the 500–600 nm. Self-assembly induced by introduction of a poor solvent allows for a spectacular shift of the emission into the near-infrared (NIR, 650–750 nm) by formation of well-defined rotationally displaced dimers. Therefore, we are here presenting a versatile platform whose optical properties can be simply tuned by self-assembly or by functionalization of the electron-deficient aromatic core of PDIs.

Truxene-BODIPY dyads and triads: Synthesis, spectroscopic characterization, one and two-photon absorption properties and electrochemistry

Eight green and blue BODIPY dyes, substituted by diverse truxene units, have been synthesized and fully characterized by HRMS and NMR spectroscopy as well as electrochemistry to determine their redox properties. Different substituents such as bromine, thiophene and ethynylthiophene were introduced at the 7,12-positions of the truxene units to further extend the conjugation pathway and increase their TPA properties. Their linear (one photon) and non-linear (two-photon) photophysical properties were also carefully investigated.