RESUMO
Small molecule photoswitches capable of toggling between two distinct molecular states in response to light are versatile tools to monitor biological processes, control photochemistry, and design smart materials. In this work, six novel dicyanorhodanine-based pyrrole-containing photoswitches are reported. The molecular design avails both the Z and E isomers from synthesis, where each can be isolated using chromatographic techniques. Inter- and intramolecular hydrogen bonding (H-bonding) interactions available to the E and Z isomers, respectively, uniquely impart thermal stability to each isomer over long time periods. Photoisomerization could be assessed by solution NMR and UV-vis spectroscopic techniques along with complementary ground- and excited-state computational studies, which show good agreement. Quantitative E â Z isomerization occurs upon 523 nm irradiation of the parent compound (where R = H) in solution, whereas Z â E isomerization using 404 nm irradiation offers a photostationary state (PSS) ratio of 84/16 (E/Z). Extending the π-conjugation of the pyrrole unit (where R = p-C6H4-OMe) pushes the maximum absorption to the yellow-orange region of the visible spectrum and allows bidirectional quantitative isomerization with 404 and 595 nm excitation. Comparator molecules have been prepared to report how the presence or absence of H-bonding affects the photoswitching behavior. Finally, studies of the photoswitches in neat films and photoinactive polymer matrices reveal distinctive structural and optical properties of the Z and E isomers and ultimately afford reversible photoswitching to spectrally unique PSSs using visible light sources including the Sun.
RESUMO
A straightforward route to 1,4-dihydropyrrolo[3,2-b]pyrroles comprised of two electron-withdrawing quinoline or tetrazolo[1,5-a]quinoline scaffolds has been developed. The versatile multicomponent reaction affording 1,4-dihydropyrrolo[3,2-b]pyrroles combined with intramolecular direct arylation enables assembly of these products in just three steps from anilines with overall yields exceeding 30%. The planarized, ladder-type heteroacenes possess up to 14 conjugated rings. These nominally quadrupolar materials exhibit efficient fluorescence with wavelengths spanning most of the visible spectrum from green-yellow for the dyes possessing biaryl bridges and orange-red for the fully fused systems. In many cases, the fluorescence quantum yields are large, the solvatofluorochromic effects are strong, and the fluorescence is maintained even in crystalline state. Analysis of the electronic structure of these molecular architectures using quantum chemical methods suggests that the character and position of the flanking heterocycle determine the shape of HOMO and LUMO and their extension to N-aryl substituents, influencing the values of molar absorption coefficient. An experimental study of the two-photon absorption (2PA) properties has revealed that it occurs in the 700-800 nm range with apparent deviation from the Laporte parity selection rule, which may be attributed to Hertzberg-Teller contribution to vibronically allowed 2PA transition.
RESUMO
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. The ability to change the structure of original rhodol chromophore into π-expanded merocyanines translates to a comprehensive method for the modulation of photophysical properties, such as shifting the absorption and emission bands across almost the entire visible spectrum, reaching a huge Stokes shift i. e. 4800â cm-1 , brightness approximately 80.000â M-1 â cm-1 , two-photon absorption cross-section above 150â GM and switching-on/off solvatofluorochromism. A detailed investigation allowed to rationalize the different spectroscopic behavior of rhodols and new merocyanines, addressing solvatochromism and two-photon absorption.
RESUMO
Here, we present a ditopic ion-pair sensor, B1, containing the BODIPY reporter unit in its structure, which is shown to be able-thanks to the presence of two heterogeneous binding domains-to interact with anions in an enhanced manner in the presence of cations. This enables it to interact with salts even in 99% aqueous solutions, making B1 a good candidate in terms of visual salt detection in the aquatic environment. Receptor B1's ability to extract and release salt was applied in the transport of potassium chloride through a bulk liquid membrane. Working with a concentration of B1 in the organic phase and with the presence of a specific salt in an aqueous solution, an inverted transport experiment was also demonstrated. By varying the type and the amount of the anions added to B1, we were able to develop diverse optical responses, including a unique four-step ON1-OFF-ON2-ON3 output.
Assuntos
Cloreto de Sódio , Água , Ânions/química , Cátions/química , Cloreto de Potássio , CorantesRESUMO
Hybrids of short oligourea foldamers with residues of α, ß and γ-amino acids esters at the C-terminus were obtained and subjected to a reaction with LiOH. There are two possible transformations under such conditions, one of which is ester hydrolysis and the formation of a carboxylic group and the other is the cyclization reaction after abstraction of a proton from urea by a base. We have investigated this reaction with difference C-terminal residue structures, as well as under different work-up conditions, especially for oligourea hybrids with α-amino acid esters. For these compounds, an oligourea-hydantoin combination is the product of cyclization. The stability of the hydantoin ring under alkaline conditions has been alsotested. Furthermore, this work reports data related to the structure of C-terminal-modified oligourea foldamers in solution and, for one compound, in the solid state. Helical folding is preserved both for cyclized and linear modifications, with oligourea-acid hybrids appearing to be more conformationally stable, as they are stabilized by an additional intramolecular hydrogen bond in comparison to cyclic derivatives.
Assuntos
Ésteres , Ureia , Modelos Moleculares , Ureia/química , Aminoácidos/química , CiclizaçãoRESUMO
A series of 15 new derivatives of 6-acetyl-7-hydroxy-4-methylcoumarin containing a piperazine group were designed with the help of computational methods and were synthesized to study their affinity for the serotonin 5-HT1A and 5-HT2A receptors. Among them, 6-acetyl-7-{4-[4-(3-bromophenyl)piperazin-1-yl]butoxy}-4-methylchromen-2-one (4) and 6-acetyl-7-{4-[4-(2-chlorophenyl)piperazin-1-yl]butoxy}-4-methylchromen-2-one (7) exhibited excellent activity for 5-HT1A receptors with Ki values 0.78 (0.4-1.4) nM and 0.57 (0.2-1.3) nM, respectively, comparable to the Ki values of 8-OH-DPAT (0.25 (0.097-0.66) nM). The equilibrium dissociation constant values of the tested compounds showed differential intrinsic activities of the agonist and antagonist modes.
Assuntos
Compostos Heterocíclicos , Serotonina , Receptor 5-HT1A de Serotonina , Receptores de Serotonina , Receptores 5-HT1 de Serotonina , Piperazinas/farmacologia , Receptor 5-HT2A de SerotoninaRESUMO
The tandem intramolecular hydroarylation of alkynes accompanied by a 1,2-aryl shift is described. Harnessing the unique electron-rich character of 1,4-dihydropyrrolo[3,2-b]pyrrole scaffold, we demonstrate that the hydroarylation of alkynes proceeds at the already occupied positionsâ 2 and 5 leading to a 1,2-aryl shift. Remarkably, the reaction proceeds only in the presence of cationic gold catalyst, and it leads to heretofore unknown π-expanded, centrosymmetric pyrrolo[3,2-b]pyrroles. The utility is verified in the preparation of 13â products that bear six conjugated rings. The observed compatibility with various functional groups allows for increased tunability with regard to the photophysical properties as well as providing sites for further functionalization. Computational studies of the reaction mechanism revealed that the formation of the six-membered rings accompanied with a 1,2-aryl shift is both kinetically and thermodynamically favourable over plausible formation of products containing 7-membered rings. Steady-state UV/Visible spectroscopy reveals that upon photoexcitation, the prepared S-shaped N-doped nanographenes undergo mostly radiative relaxation leading to large fluorescence quantum yields. Their optical properties are rationalized through time-dependent density functional theory calculations. We anticipate that this chemistry will empower the creation of new materials with various functionalities.
RESUMO
ß-Hydroxy sulfones are important in organic synthesis. The simplest method of ß-hydroxy sulfones synthesis is the hydrogenation of ß-keto sulfones. Herein, we report the reducing properties of alkyl aluminum compounds R3Al (R = Et, i-Bu, n-Bu, t-Bu and n-Hex); i-Bu2AlH; Et2AlCl and EtAlCl2 in the hydrogenation of ß-keto sulfones. The compounds i-Bu2AlH, i-Bu3Al and Et3Al are the at best reducing agents of ß-keto sulfones to ß-hydroxy sulfones. In reactions of ß-keto sulfones with aluminum trialkyls, hydroalumination products with ß-hydroxy sulfone ligands [R2AlOC(C6H5)CH2S(O)2(p-R1C6H4]n [where n = 1,2; 2aa: R = i-Bu, R1 = CH3; 2ab: R = i-Bu, R1 = Cl; 2ba: R = Et, R1 = CH3; 2bb: R = Et, R1 = Cl] and {[Et2AlOC(C6H5)CH2S(O)2(p-ClC6H4]âEt3Al}n3bb were obtained. These complexes in the solid state have a dimeric structure, while in solutions, they appear as equilibrium monomer-dimer mixtures. The hydrolysis of both the isolated 2aa, 2ab, 2ba, 2bb and 3bb and the postreaction mixtures quantitatively leads to pure racemic ß-hydroxy sulfones. Hydroalumination reaction of ß-keto sulfones with alkyl aluminum compounds and subsequent hydrolysis of the complexes is a simple and very efficient method of ß-hydroxy sulfones synthesis.
Assuntos
Alumínio , Sulfonas , Alumínio/química , Compostos de Alumínio , Hidrogenação , Estrutura Molecular , Sulfonas/químicaRESUMO
A 4-nitro-L-phenylalanine scaffold was used to construct effective ion pair receptors capable of binding anions in an enhanced manner with the assistance of alkali metal cations. A benzocrown ether was linked to a receptor platform via the amide function so as to support the squaramide function in anion binding and to allow all three NHs to act simultaneously. The binding properties of the receptors were determined using UV-vis, 1H NMR, 2D NMR, and DOSY spectroscopy in MeCN and in the solid state by X-ray measurements. Ion pair receptor 2 was found to interact with the most strongly with salts, and the removal of its key structural elements was shown to hinder the receptor action. The amide proton was recognized to switch from having involvement in an intramolecular hydrogen bond to interacting with anions upon complexation. Apart from carboxylates, which promote deprotonation, and other monovalent salts creating 1:1 complexes with the receptor, more complex equilibria were established upon the complexation of 2 with sulfates. Receptor 2 was shown to be capable of the extraction of ion pairs from the aqueous to organic phase and of the cation-enhanced transport chloride and sulfate anions across a bulk chloroform membrane. These features may open the door for its use in regulating ion concertation under interfacial conditions and acting as a potential drug to treat channelopathies.
Assuntos
Aminoácidos/metabolismo , Ânions/metabolismo , Cátions/metabolismo , Sais/metabolismo , Sulfatos/metabolismo , Aminoácidos/química , Ânions/química , Cátions/química , Cristalografia por Raios X , Ligação de Hidrogênio , Modelos Moleculares , Estrutura Molecular , Sais/química , Sulfatos/químicaRESUMO
In contrast to monotopic receptor 3, the anthracene functionalized squaramide dual-host receptor 1 is capable of selectively extracting sulfate salts, as was evidenced unambiguously by DOSY, mass spectrometry, fluorescent and ion chromatography measurements. The receptors were investigated in terms of anion and ion pair binding using the UV-vis and 1H NMR titrations method in acetonitrile. The reference anion receptor 3, lacking a crown ether unit, was found to lose the enhancement in anion binding induced by the presence of cations. Besides the ability to bind anions in an enhanced manner exhibited by ion pair receptors 2 and 4, changing the 1-aminoanthracene substituent resulted in their exhibiting a lower anion affinity than receptor 1. By using receptor 1 and adjusting the water content in organic phase it was possible to selectively detect sulfates both by "turn-off" and "turn-on" fluorescence, and to do so homogenously and under interfacial conditions. Such properties of receptor 1 have allowed the development of a new type of sensor capable of recognizing and extracting potassium sulfate from the aqueous medium across a phase boundary, resulting in an appropriate fluorescent response in the organic solution.
Assuntos
Ânions/química , Antracenos/química , Acetonitrilas/química , Cátions/química , Éteres de Coroa/química , Cristalografia por Raios X/métodos , Fluorescência , Ligação de Hidrogênio , Espectroscopia de Ressonância Magnética/métodos , Modelos Moleculares , Quinina/análogos & derivados , Quinina/química , Sulfatos/químicaRESUMO
A bowl-shaped nitrogen-doped nanographene composed of a pyrrolo[3,2-b]pyrrole core substituted with six arene rings circularly bonded with one another has been prepared via a concise synthetic strategy encompassing the multicomponent tetraarylpyrrolopyrrole (TAPP) synthesis, the Scholl reaction, and intramolecular direct arylation. This synthesis represents the first case of programmed sequential intramolecular direct arylation reactions utilizing the different reactivity of C-Br and C-Cl bonds. The target compound contains two central pentagons confined between two adjacent heptagons-the inverse Stone-Thrower-Wales topology. The presence of both five- and seven-membered rings in the final structure is responsible for interesting properties such as a perpendicularly aligned dipole moment, absorption and fluorescence in the orange-red region, weak emission originating from the charge-transfer character of a low-energy absorption band, and a high lying HOMO. In the solid state slipped convex-to-convex π-π stacking dominates.
RESUMO
The use of a squaramide-based ion pair receptor offers a solution to the very challenging problem of extraction and transport of extremely hydrated sulfate salt. Herein we demonstrate for the first time that a neutral receptor is able not only to selectively extract but also to transport sulfates in the form of an alkali metal salt across membranes and to do so in a cooperative manner while overcoming the Hofmeister bias. This was made possible by an enhancement in anion binding promoted by cation assistance and by diversifying the stoichiometry of receptor complexes with sulfates and other ions. The existence of a peculiar 4:1 complex of receptor 2 with sulfates in solution was confirmed by UV-vis and 1H NMR titration experiments, DOSY and DLS measurements, and supported by solid-state X-ray measurements. By varying the separation technique and experimental conditions, it was possible to switch the depletion of the aqueous layer into extremely hydrophilic or less lipophilic salts, thus obtaining the desired selectivity.
RESUMO
A tripodal, squaramide-based ion-pair receptor 1 was synthesized in a modular fashion, and 1H NMR and UV-vis studies revealed its ability to interact more efficiently with anions with the assistance of cations. The reference tripodal anion receptor 2, lacking a crown ether unit, was found to lose the enhancement in anion binding induced by presence of cations. Besides the ability to bind anions in enhanced manner by the "single armed" ion-pair receptor 3, the lack of multiple and prearranged binding sites resulted in its much lower affinity towards anions than in the case of tripodal receptors. Unlike with receptors 2 or 3, the high affinity of 1 towards salts opens up the possibility of extracting extremely hydrophilic sulfate anions from aqueous to organic phase. The disparity in receptor 1 binding modes towards monovalent anions and divalent sulfates assures its selectivity towards sulfates over other lipophilic salts upon liquid-liquid extraction (LLE) and enables the Hofmeister bias to be overcome. By changing the extraction conditions from LLE to SLE (solid-liquid extraction), a switch of selectivity from sulfates to acetates was achieved. X-ray measurements support the ability of anion binding by cooperation of the arms of receptor 1 together with simultaneous binding of cations.
Assuntos
Acetatos/química , Ânions/química , Cátions/química , Extração Líquido-Líquido , Quinina/análogos & derivados , Receptores Artificiais/síntese química , Extração em Fase Sólida , Sulfatos/química , Sítios de Ligação , Éteres de Coroa/química , Cristalografia por Raios X , Ligação de Hidrogênio , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Quinina/química , Receptores Artificiais/química , Sódio/química , Espectrofotometria Ultravioleta , Ácido Trifluoracético/químicaRESUMO
We synthesized an ion pair receptor 1 consisting of a crown ether cation binding site and a squaramide anion binding domain and compared its binding properties to those of its analogous urea counterpart 2. We studied their salt binding properties using spectrophotometric and spectroscopic measurements in an acetonitrile solution and in acetonitrile/water mixtures. Apart from carboxylate anions, all of the anions tested were found to associate with receptor 1 and 2 more strongly in the presence of sodium cations. A homotopic anion receptor 3, lacking a crown ether unit, was unable to bind sodium salt more strongly than tetrabutylammonium salts. Solution and solid-state X-ray measurements revealed strong sodium chloride coordination to receptor 1, which is able to bind this salt even in the presence of 10% water. In contrast to the urea-based ion pair receptor 2 or anion receptor 3, ditopic receptor 1 is capable of extracting sodium chloride from aqueous media to the organic phase, as was evidenced unambiguously by 1H nuclear magnetic resonance, mass spectrometry, and atomic absorption spectroscopy analyses.
RESUMO
In this paper we present the synthesis and reactivity of dithiols comprising of two cysteine moieties attached to a dipicolinic acid core. Oxidation of these thiols provides oligomeric macrocycles. Monomers with 13-membered rings are kinetic products which are, however, strained and readily transform into higher oligomers under basic conditions or elevated temperature via a disulphide exchange reaction. Dimers, which are the most stable thermodynamic products, equilibrate only under inert conditions with thiolate as a catalyst. Under aerobic conditions, the thiols are oxidised before the equilibrium is reached.
RESUMO
The synthesis of a weakly coupled, strongly polarized coumarin dimer has been achieved for the first time. The three-step strategy comprises the Skattebøl formylation followed by the Knoevenagel reaction and the formation of a tertiary amide by using a peptide-type procedure. The molecule consists of two different coumarin moieties: One is a classical donor-acceptor system and the second one possesses a weaker amide donor at the 7-position. The polarized coumarin dimer can form an electronically conjugated structure possessing an electric dipole larger than that of 7-(dimethylamino)coumarin-3-carboxylic acid. The limited flexibility of the inter-coumarin connection results in stable conformers of different electric dipole moments and complex photophysics. In the solid state, this compound has a strongly bent conformation with the two coumarin units forming an angle of around 74°. In solution, two conformers are in equilibrium. The existence of the molecule as two conformers in the ground state has been confirmed by optical studies, and further corroborated by molecular calculations. The fluorescence spectra possess a unique feature: A charge-transfer band (ca. 550â nm) is visible only in nonpolar or weakly polar solvents. Optical spectroscopy studies coupled with molecular calculations allowed us to rationalize this phenomenon: The large amplitude of intramolecular motions is responsible for the conformational isomerization as well as producing a conical intersection between the potential energy surfaces of the excited singlet state and the ground state, which opens an internal conversion channel that effectively competes with the fluorescence of the conformers.
Assuntos
Cumarínicos/química , Modelos Moleculares , Luz , Espectroscopia de Ressonância Magnética/métodos , Conformação Molecular , Estrutura Molecular , Solventes/química , Espectrometria de Fluorescência/métodos , Estereoisomerismo , Relação Estrutura-AtividadeRESUMO
trans-A2 B-Corroles with amide substituents at different positions versus the macrocyclic core have been synthesized. Their self-organizing properties have been comprehensively evaluated both in solid-state and in solution. The rigid arrangement of the amide functionality with the corrole ring led to the formation of strong intramolecular interactions and precluded intermolecular interactions. Replacement of sterically hindered C6 F5 substituents at positions 5 and 15 with smaller electron-withdrawing CO2 Me groups resulted in significant changes in the self-assembly pattern. With these substituents, tetramers formed in a crystalline state, in which one of the H-pyrrole subunits is out of the corrole plane. This allows the N-H group to form a hydrogen bond with a neighboring carbonyl group of the n-butyl amide fragment. DOSY NMR studies showed that amido-corroles bearing the OCH2 CONHnBu motif formed dimers in millimolar solutions in nonpolar solvents and the dimers existed in equilibrium with monomers. However, the corroles possessing meso-ester groups did not form dimers in polar tetrahydrofuran. Comprehensive optical studies allowed the absorption and emission features of the monomer corroles to be characterized in dilute solutions.
RESUMO
We report a new efficient way of synthesizing high-purity hydrogen-rich M(BH3NH2BH2NH2BH3) salts (M = Li, Na, K, Rb, Cs). The solvent-mediated metathetic synthesis applied here uses precursors containing bulky organic cations and weakly coordinating anions. The applicability of this method permits the entire series of alkali-metal M(BH3NH2BH2NH2BH3) salts (M = Li, Na, K, Rb, Cs) to be obtained, thus enabling their comparative analysis in terms of crystal structures and hydrogen-storage properties. A novel polymorphic form of Verkade's base (C18H39N4PH)(BH3NH2BH2NH2BH3) precursor was also characterized structurally. For all compounds, we present a comprehensive structural, spectroscopic, and thermogravimetric characterization (PXRD, NMR, FTIR, Raman, and TGA/DSC/MS).
RESUMO
The dilution of tert-butylamine (tBA) with water and subsequent cooling leads to a large series of different crystalline hydrates by an inâ
situ IR laser melting-zone procedure. The crystal structures were determined for tBAâ
n H2 O, with n=0, 1/4, 1, 7 1/4, 7 3/4, 9 3/4, 11, and 17. For the two lower hydrates (n= 1/4, 1), one- and two-dimensional hydrogen-bonded networks are formed, respectively. The higher hydrates (n>1) exhibit a clathrate-like three-dimensional water framework with the tBA molecules as part of, or sitting inside, the cages. In all cases, tBA is hydrogen-bonded to the H2 O framework. In the intermediate range (1
RESUMO
A series of arylpiperazine derivatives of 1,16-diphenyl-19-azahexacyclo-[14.5.1.02,15.03,8.09,14.017,21]docosa-2,3,5,7,8,9,11,13,14-nonaene-18,20,22-trione and 4,10-diphenyl-1H,2H,3H,5H-indeno[1,2-f]isoindole-1,3,5-trione was synthesized. The pharmacological profile of compound 4 at the 5-HT1A receptor was measured by binding assay. The title compounds were tested in cell-based assay against the human immunodeficiency virus type-1. The X-ray crystallographic studies of derivatives 2, 6, 7, 11, 19, and 20 were presented.