Fluorimetric Detection of Vapor Pollutants with Diketopyrrolopyrrole Polymer Microcavities.

The increasing prevalence and detrimental effects of volatile organic compounds are driving the need for selective on-site sensors that do not require complex sampling or instrumentation. Broadband selective sensors exhibiting selectivity based on their distinct response mechanism is becoming of increasing technological relevance in both industrial and urban settings. In this context, we propose a label-free sensor based on a polymeric planar microcavity embedded with a fluorescent organic dye, designed to detect various pollutants in the vapor phase.

The magic of biaryl linkers: the electronic coupling through them defines the propensity for excited-state symmetry breaking in quadrupolar acceptor-donor-acceptor fluorophores.

Charge transfer (CT) is key for molecular photonics, governing the optical properties of chromophores comprising electron-rich and electron-deficient components. In photoexcited dyes with an acceptor-donor-acceptor or donor-acceptor-donor architecture, CT breaks their quadrupolar symmetry and yields dipolar structures manifesting pronounced solvatochromism. Herein, we explore the effects of electronic coupling through biaryl linkers on the excited-state symmetry breaking of such hybrid dyes composed of an electron-rich core, , 1,4-dihydropyrrolo[3,2-]pyrrole (DHPP), and pyrene substituents that can act as electron acceptors.

Conformation of the Ester Group Governs the Photophysics of Highly Polarized Benzo[]coumarins.

Photosensitizers that display "unusual" emission from upper electronically excited states offer possibilities for initiating higher-energy processes than what the governing Kasha's rule postulates. Achieving conditions for dual fluorescence from multiple states of the same species requires molecular design and conditions that favorably tune the excited-state dynamics. Herein, we switch the position of the electron-donating NMe group around the core of benzo[]coumarins (BgCoum) and tune the electronic coupling and the charge-transfer character of the fluorescent excited states.

Novel Method for the Synthesis of Merocyanines: New Photophysical Possibilities for a Known Class of Fluorophores.

A new, transformative method for the preparation of rhodols and other merocyanines from readily available tetrafluorohydroxybenzaldehyde and aminophenols has been developed. It is now possible to prepare merocyanines bearing three fluorine atoms and additional conjugated rings, and the whole one-pot process occurs under neutral, mild conditions. Three heretofore unknown merocyanine-based architectures were prepared using this strategy from aminonaphthols and 4-hydroxycoumarins.

All-Polymer Microcavities for the Fluorescence Radiative Rate Modification of a Diketopyrrolopyrrole Derivative.

Controlling the radiative rate of emitters with macromolecular photonic structures promises flexible devices with enhanced performances that are easy to scale up. For instance, radiative rate enhancement empowers low-threshold lasers, while rate suppression affects recombination in photovoltaic and photochemical processes. However, claims of the Purcell effect with polymer structures are controversial, as the low dielectric contrast typical of suitable polymers is commonly not enough to provide the necessary confinement.

The Synthesis and Photophysical Properties of Weakly Coupled Diketopyrrolopyrroles.

Three centrosymmetric diketopyrrolopyrroles possessing either two 2-(2'-methoxyphenyl)benzothiazole or two 2-(2'-methoxyphenyl)benzoxazolo-thiophene scaffolds were synthesized in a straightforward manner, and their photophysical properties were investigated. Their emission was significantly bathochromically shifted as compared with that of simple DPPs reaching 650 nm. Judging from theoretical calculations performed with time-dependent density functional theory, in all three cases the excited state was localized on the DPP core and there was no significant CT character.

Langmuir-Blodgett Films of Diketopyrrolopyrroles with Tunable Amphiphilicity.

In this work, we present the formation of H- and J-aggregates of amphiphilic centrosymmetric diketopyrrolopyrroles containing aliphatic or aromatic amino groups. The inherent amphiphilicity of these dyes predestines their assembly at interfaces to form ordered supramolecular structures. In this work, we employed the Langmuir-Blodgett (LB) technique to generate, manipulate, and deposit such supramolecular structures.

Access to Corrole-Appended Persubstituted Benzofurans by a Multicomponent Reaction: The Dual Role of -Chloranil.

A multicomponent reaction among dipyrranes, aryl-propargyl aldehydes, and -chloranil leading to 10-(benzofuran-2-yl)corroles is described. -Chloranil was identified as a crucial reagent playing a twofold role: an oxidant taking part in the formation of the corrole macrocycle and a component undergoing heteroannulation to the incipient 10-arylethynylcorrole. A series of corroles bearing persubstituted benzofuran-2-yl moieties have been synthesized, and their fundamental electronic properties have been studied via UV-vis absorption and fluorescence spectroscopies.

Method for the Large-Scale Synthesis of Multifunctional 1,4-Dihydro-pyrrolo[3,2-]pyrroles.

A thorough investigation has enabled the optimization of the synthesis of 1,4-dihydro-pyrrolo[3,2-]pyrroles. Although salts of such metals as vanadium, niobium, cerium, and manganese were found to facilitate the formation of 1,4-dihydro-pyrrolo[3,2-]pyrroles from amines, aldehydes, and diacetyl, we confirmed that iron salts are the most efficient catalysts. The conditions identified (first step: toluene/AcOH = 1:1, 1 h, 50 °C; second step: toluene/AcOH = 1:1, Fe(ClO)·HO, 16 h, 50 °C) resulted in the formation of tetraarylpyrrolo[3,2-]pyrroles in a 6-69% yield.

High-speed two-photon polymerization 3D printing with a microchip laser at its fundamental wavelength.

High-resolution, high-speed 3D printing by two-photon polymerization (2PP) with a Nd:YVO Q-switched microchip laser at its fundamental wavelength of 1064 nm is demonstrated. Polymerization scan speeds of up to 20 mm/s and feature sizes of 250 nm are achieved using a high repetition rate Q-switched microchip laser with a semiconductor saturable absorber mirror (SESAM) and photoresist with a new photo-initiator bearing 6-dialkylaminobenzufuran as electron donor and indene-1,3-dione moiety as electron acceptor. The obtained results demonstrate the high potential of Q-switched microchip lasers for applications in 2PP 3D printing.

π-Conjugated Organic-Inorganic Hybrid Photoanodes: Revealing the Photochemical Behavior through In Situ X-Ray Absorption Spectroscopy.

Small-molecule organic semiconductors exhibit great potential for the photoelectrochemical oxidation of water because of their n-type semiconductor nature and their tunable bandgaps. In this work, several head-to-tail bis-coumarins were synthesized and their photophysical properties characterized. Their characteristics as n-type semiconductors were modified by varying the electronic character of substituents at positions 1 and 7, which enabled the energy level of the LUMO and the photoinduced charge-carrier-transfer efficiency to be modulated.

Self-assembling corroles.

trans-A2B-corroles bearing -OCH2CONHR groups at the ortho position of the meso-phenyl substituent undergo self-organization both in the solid state as well as in solution. The lack of additional donor atoms induces sheet formation, but if the pyridine unit is present in the structure, more complex helical forms are formed.

Insights into the tautomerism in meso-substituted corroles: a variable-temperature 1H, 13C, 15N, and 19F NMR spectroscopy study.

Tris(pentafluorophenyl)corrole and its (15)N-enriched isotopomer were studied in [D8]toluene solution by 1D and 2D variable-temperature NMR techniques to establish the mechanisms of tautomerization of the NH protons inside the interior of the corrole macrocycle. Three such rate processes could be identified of which two modulate the spectral line shapes at temperatures above 205 K and the third is NMR-inaccessible as it is very fast. The latter involves the proton engaged in an unsymmetrical proton sponge unit formed by two pyrrole nitrogen atoms.

Synthesis of lithium corrole and its use as a reagent for the preparation of cyclopentadienyl zirconium and titanium corrole complexes.

The lithium corrole complex (Mes(2)(p-OMePh)corrole)Li(3)·6THF (1·6THF), prepared via deprotonation of the free-base corrole with lithium amide, acts as precursor for the preparation of cyclopentadienyl zirconium(iv) corrole (2) and pentamethylcyclopentadienyl titanium(IV) corrole (3).

Synthesis of trans-A2B2-porphyrins bearing phenylethynyl substituents.

Efficient and convenient conditions for the preparation of trans-A(2)B(2)-porphyrins bearing two phenylethynyl moieties directly from phenylpropargyl aldehydes and dipyrromethanes of diversified lipophilicity and reactivity have been developed. This new procedure allows the preparation of a library of porphyrins of this architecture with a wide range of substituents. Thanks to the identification of the reagent solubility as one of the key factors influencing the yield of the porphyrinogens, we were able to improve yields to ca.

Palladium-catalyzed 2-arylation of pyrroles.

A methodology that affords N-alkyl-2-arylpyrroles and N-aryl-2-arylpyrroles via direct coupling from aryl iodides has been developed. After examining various reaction parameters: solvent, ratio of reagents, catalyst, base and additives the optimal conditions for the condensation were identified. Two crucial factors, (a) anhydrous DMSO as solvent and (b) 5 M excess of pyrrole counterpart, were found to strongly influence the reaction outcome.

Meso-meso linked corroles.

The cascade reaction of sterically hindered dipyrromethanes and formaldehyde furnished meso(10)-meso(10') linked corroles--a new type of porphyrinoid--compounds with interesting photophysical properties.

Efficient synthesis of meso-substituted corroles in a H2O-MeOH mixture.

New and efficient conditions for the synthesis of meso-substituted corroles were developed. The first step, involving the reaction of aldehydes with pyrrole, was carried out in a water-methanol mixture in the presence of HCl. A relatively narrow distribution of aldehyde-pyrrole oligocondensates was obtained through careful control of their solubility in the reaction medium.

Electrochemistry and spectroelectrochemistry of meso-substituted free-base corroles in nonaqueous media: reactions of (Cor)H3, [(Cor)H4]+, and [(Cor)H2]-.

Eleven free-base corroles with different electron-donating or electron-withdrawing meso substituents were characterized as to their electrochemistry and UV-visible spectroscopy in benzonitrile (PhCN) or pyridine containing tetra-n-butylammonium perchlorate (0.1 M). Six forms of the compounds with different numbers of protons and/or oxidation states were spectroscopically identified and are represented as (Cor)H3, (.

The synthesis and properties of bis-1,1'-(porphyrinyl)ferrocenes.

Ferrocene-bridged bisporphyrins have been synthesized by the condensation of corresponding dipyrromethane-derived diols with a bisdipyrromethane. Purification of the final compounds has been achieved without chromatography. The specific geometry of these bisporphyrins makes them valuable starting points for building complex molecular and supramolecular structures.

Refined methods for the synthesis of meso-substituted A3- and trans-A2B-corroles.

We have refined a one-pot synthesis of A3-corroles via "3 + 4" condensation of an aldehyde with a pyrrole followed by macrocyclization mediated by DDQ. After thorough examination of various reaction parameters (reactivity of an aldehyde, catalyst, solvent, concentration, time etc.) we have elaborated three different sets of conditions for different types of aromatic aldehydes--highly reactive, moderately reactive and sterically hindered.

Synthesis of corroles bearing up to three different meso substituents.

[reaction: see text] We have developed a new method that affords regioisomerically pure corroles possessing up to three different substituents at the meso positions. The corrole formation reaction involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol with pyrrole followed by oxidation with DDQ. ABC-Type corroles were synthesized for the first time according to this procedure.