Apolar Solvents Research Articles

Synthesis and Photophysical Properties of 4'-5' Disubstituted CinNapht Dyes Accessible through Double SNAr Late-Stage Functionalization.

This article describes the synthesis of a difluorinated CinNapht derivative in the 4' and 5' positions allowing the easy access to two new families of fluorophores by late-stage functionalization using SNAr. The first one comprises derivatives incorporating hindered aromatic amines in the 4' and 5' positions, which show redemission in apolar solvents. The second one is obtained through the use of dinucleophiles. Among them, Tetrahydroquinoxaline (THQ) and tetrahydrobenzodiazepine (THB) compounds show strongly redshifted emission. The photophysical properties of all the fluorophores in these two families are studied and rationalized by DFT and TDDFT calculations. The most promising compounds have been used to image living cells by confocal microscopy.

Mild and Scalable Conditions for the Solvothermal Synthesis of Imine‐Linked Covalent Organic Frameworks

AbstractA convenient method was developed that allows for the synthesis of highly crystalline and porous imine‐linked covalent organic frameworks (COFs) in hours. The use of an apolar solvent in combination with a precise amount of water and acetic acid was crucial to obtain materials of optimal quality. Fifteen different COFs could be produced under the same reaction conditions, using a green solvent mixture of n‐butanol, acetic acid and water at 70 °C for 16 hours with stirring. The crystallinity of the COFs produced in this manner is similar or better than that obtained by traditional solvothermal synthesis. The method could be easily scaled to synthesize over ten grams of COF in one batch. Optical microscopy, FTIR spectroscopy and in situ Raman spectroscopy gave insight in the role of the solvent on the aggregation of COF nanosheets and the resulting crystallinity, porosity and robustness of the material.

Long-Lived Charge Carrier Photogeneration in a Cooperative Supramolecular Double-Cable Polymer.

A newly designed C3-symmetric disc-shaped chromophore, BTT(NDI)3, features electron accepting naphthalene diimides linked to an electron donor BTT core. BTT(NDI)3 self-assembles in apolar solvents into highly ordered, chiral supramolecular fibers through π-π and 3-fold hydrogen-bonding interactions. This leads to a cooperative formation of plane-to-plane stacking of BTTs and J-aggregation of the outer NDIs. Such a structure ensures high charge mobility. Only photoexcitation of BTT in the BTT(NDI)3 polymers triggers a unidirectional electron transfer from BTT to NDI and results in (BTT•+-NDI•-) lifetimes that are by up to 3 orders of magnitude longer compared to (NDI•+-NDI•-) that is formed upon NDI photoexcitation. A multiphasic decay implies ambipolar pathways for charge carriers, that is, electron and hole delocalization along the respective BTT and NDI stacks. Our supramolecular approach offers potential for developing functional supramolecular polymers with continuous pathways for electrons and holes and, in turn, minimizing charge recombination losses in organic photovoltaic devices.

Simultaneous Imaging of Temperature and Oxygen by Utilizing Thermally Activated Delayed Fluorescence and Phosphorescence of a Single Indicator.

Chemical gradients are essential in biological systems, affecting processes like microbial activity in soils and nutrient cycling. Traditional tools, such as microsensors, offer high-resolution data but are limited to one-dimensional measurements. Planar optodes allow for two-dimensional (2D) and three-dimensional (3D) chemical imaging but are often sensitive to temperature changes. This study presents an advanced dual-emission optical sensor that simultaneously measures temperature and oxygen using a modified platinum(II) meso-tetrakis(3,5-ditert-butylphenyl)-tetra(2-tert-butyl-1,4-naphthoquinono)porphyrin. The ratio between thermally activated delayed fluorescence and phosphorescence was optimized by modifying platinum(II) naphthoquinonoporphyrin with tert-butyl groups which simultaneously improved solubility in apolar solvents and polymer matrix (polystyrene). This dual-function sensor enables two-parameter chemical imaging with a consumer-grade RGB camera or a hyperspectral camera. We demonstrated 2D visualization of temperature and oxygen distribution in a model soil system. The RGB camera provided rapid and cost-effective imaging, while the hyperspectral camera offered more detailed spectral information despite some limitations. Our findings revealed the formation of a stable temperature gradient and oxygen depletion, driven by water content and temperature-sensitive microbial activity. This dual O2/T sensor, with further potential improvements, shows considerable promise for advanced multiparameter sensing in complex biological and environmental studies, providing deeper insights into dynamic microenvironments.

Structural Fine‐Tuning to Achieve Highly Fluorescent Organic and Water‐Soluble Thiazolo[5,4‐d]thiazole Chromophores

AbstractFluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid‐state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge‐transfer (ICT) in a family of unsymmetrical donor‐thiazolo[5,4‐d]thiazole‐acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution‐state fluorescence quantum yield (>80 %) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor‐π‐acceptor systems.

Structural Fine-Tuning to Achieve Highly Fluorescent Organic and Water-Soluble Thiazolo[5,4-d]thiazole Chromophores.

Fluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid-state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge-transfer (ICT) in a family of unsymmetrical donor-thiazolo[5,4-d]thiazole-acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution-state fluorescence quantum yield (>80 %) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor-π-acceptor systems.

Flexible, Photonic Films of Surfactant‐Functionalized Cellulose Nanocrystals for Pressure and Humidity Sensing

Most paints contain pigments that absorb light and fade over time. A robust alternative can be found in nature, where structural coloration arises from the interference of light with submicron features. Plant‐derived, cellulose nanocrystals (CNCs) mimic these features by self‐assembling into a cholesteric liquid crystal that exhibits structural coloration when dried. While much research has been done on CNCs in aqueous solutions, less is known about transferring CNCs to apolar solvents that are widely employed in paints. This study uses a common surfactant in agricultural and industrial products to suspend CNCs in toluene . Surprisingly, a stable liquid crystal phase is formed within hours, even with concentrations of up to 50 wt%. Evaporating the apolar CNC suspensions results in photonic films with peak wavelengths ranging from 660 to 920 nm. The resulting flexible films have variable mechanical properties with surfactant content, allowing for an optical response with applied force. The films also act as humidity sensors, with increasing relative humidity swelling the films, yielding a redshift in the reflected wavelength. With the addition of a single surfactant, CNCs can be made compatible with existing production methods of industrial coatings, while improving the strength and responsiveness of structurally colored films to external stimuli.

Reversible C═N Bond Formation Controls Charge-Separation in an Aza-Diarylethene Photoswitch.

Diarylethenes belong to the most eminent photoswitches and have been studied for many decades. They are found in virtually every field of application and have become highly valuable molecular tools for instilling light-responsiveness into materials, catalysts, biological systems, or pharmacology. In this work, we present a novel and distinct type of pyrimidine-based aza-diarylethene, which undergoes a highly unusual zwitterion-forming photoreaction. During this fully reversible process, a CN double bond is established under concomitant aromatization and thiophene-ring opening. The metastable zwitterion thus possesses a positively charged extended aromatic structure and an independent conjugated thiolate function. It can further photoisomerize between a more stable Z and a less stable E isomer, resulting in effective four-state photoswitching. Unusual for diarylethenes, the metastable isomers show negative solvatochromism and red-shifted absorption in apolar solvents. With this behavior, aza-diarylethenes effectively bridge the properties of merocyanines and diarylethenes. Thermal stability of the zwitterions can be modulated from very labile to highly stable behavior in response to pH, again in a fully reversible manner. Pyrimidine-based aza-diarylethene thus establishes a unique photoreaction mechanism for diarylethenes, allowing control of charge separation, thermal stability, and color generation in a different way than hitherto possible.

Planar Polymer Membranes Accommodate Functional Self-Assembly of Inserted Resorcinarene Nanocapsules.

Solid-supported polymer membranes (SSPMs) offer great potential in material and life sciences due to their increased mechanical stability and robustness compared to solid-supported lipid membranes. However, there is still a need for expanding the functionality of SSPMs by combining them with synthetic molecular assemblies. In this study, SSPMs served as a flexible matrix for the insertion of resorcinarene monomers and their self-assembly into functional hexameric resorcinarene capsules. Resorcinarene capsules provide a large cavity with affinity specifically for cationic and polyhydroxylated molecules. While the capsules are stable in apolar organic solvents, they disassemble when placed in polar solvents, which limits their application. Here, a solvent-assisted approach was used for copolymer membrane deposition on solid support and simultaneous insertion of the resorcinarene monomers. By investigation of the molecular factors and conditions supporting the codeposition of the copolymer and resorcinarene monomers, a stable hybrid membrane was formed. The hydrophobic domain of the membrane played a crucial role by providing a sufficiently thick and apolar layer, allowing for the self-assembly of the capsules. The capsules were functional inside the membranes by encapsulating cationic guests from the aqueous environment. The amount of resorcinarene capsules in the hybrid membranes was quantified by a combination of quartz-crystal microbalance with dissipation and liquid chromatography-mass spectrometry, while the membrane topography and layer composition were analyzed by atomic force microscopy and neutron reflectometry. Functional resorcinarene capsules inside SSPMs can serve as dynamic sensors and potentially as cross-membrane transporters, thus holding great promise for the development of smart surfaces.

Tuning the Absorption, Fluorescence, Intramolecular Charge Transfer, and Intersystem Crossing in Spiro[fluorene]acridinone.

In this work, we prepared a series of electron donor-acceptor systems based on spiro[fluorene-9,7'-dibenzo[c,h]acridine]-5'-one (SFDBAO). Our SFDBAOs consist of orthogonally positioned fluorenes and aromatic ketones. By fine-tuning the substitution of electron-donating pyrenes, the complex interplay among different excited-state decay channels and the overall impact of solvents on these decay channels were uncovered. Placing pyrene, for example, at the aromatic ketones resulted in a profound solvatochromism in the form of a bright charge-transfer (CT) emission spanning from yellow to red-NIR. In contrast, a dark non-emissive CT was noted upon pyrene substitution at the fluorenes. In apolar solvents, efficient triplet-excited state generation was observed for all SFDBAOs. Either charge transfer was concluded to mediate the intersystem crossing (ISC) in the case of pyrene substitution or the El-Sayed rule was applicable when lacking pyrene substitution as in the case of SFABAO. In polar solvents, charge separation is the sole decay upon pyrene substitution. Moreover, competition between ISC and CT lowered the triplet-excited state generation in SFDBAO.

Tuning the Absorption, Fluorescence, Intramolecular Charge Transfer, and Intersystem Crossing in Spiro[fluorene]acridinone

AbstractIn this work, we prepared a series of electron donor‐acceptor systems based on spiro[fluorene‐9,7’‐dibenzo[c,h]acridine]‐5’‐one (SFDBAO). Our SFDBAOs consist of orthogonally positioned fluorenes and aromatic ketones. By fine‐tuning the substitution of electron‐donating pyrenes, the complex interplay among different excited‐state decay channels and the overall impact of solvents on these decay channels were uncovered. Placing pyrene, for example, at the aromatic ketones resulted in a profound solvatochromism in the form of a bright charge‐transfer (CT) emission spanning from yellow to red‐NIR. In contrast, a dark non‐emissive CT was noted upon pyrene substitution at the fluorenes. In apolar solvents, efficient triplet‐excited state generation was observed for all SFDBAOs. Either charge transfer was concluded to mediate the intersystem crossing (ISC) in the case of pyrene substitution or the El‐Sayed rule was applicable when lacking pyrene substitution as in the case of SFABAO. In polar solvents, charge separation is the sole decay upon pyrene substitution. Moreover, competition between ISC and CT lowered the triplet‐excited state generation in SFDBAO.

Activation of alkyl hydroperoxides by manganese complexes of tmtacn for initiation of radical polymerisation of alkenes.

The activation of alkyl hydroperoxides to generate radicals is a key step in the initiation of radical polymerisations in many industrial applications, not least protective coatings. Cobalt soaps (Co(ii) alkyl carboxylates) are highly effective catalysts under ambient conditions but viable alternatives based on less scarce catalysts are desirable, with especially iron and manganese catalysts showing potential. Manganese complexes of the ligand N,N',N″-trimethyl-1,4,7-triazacyclononane (tmtacn) are long established as catalysts for organic oxidations with H2O2, however their reactivity with alkyl hydroperoxides is less studied especially in apolar solvents. Here we show that this family of complexes can be employed as catalysts for the decomposition of alkyl hydroperoxides in apolar solvents such as styrene/methyl methacrylate mixtures and resins based on styrene/bisphenol-A based diglycidyl ether bismethacrylate (BADGE-MA). The progress of alkene polymerisation in crosslinking resins is followed by Raman spectroscopy to establish its dependence on the oxidation state of the manganese catalyst used, as gelation time and onset of autoacceleration are of particular interest for many applications. We show, through reaction progress monitoring with UV/vis absorption and Raman spectroscopy, that the stability of the manganese complexes in the resin mixtures has a substantial effect on curing progress and that the oxidation state of the resting state of the catalyst is most likely Mn(ii), in contrast to reactions with H2O2 as oxidant in which the oxidation state of the resting state of catalyst is Mn(iii). Manganese complexes of tmtacn are shown to be capable initiators of alkene radical polymerisations, and their rich coordination and redox chemistry means that resin curing kinetics can potentially be tuned more readily than with cobalt alkyl carboxylates.

Catalyst- and excess reagent recycling in aza-Michael additions.

16α-Azolyl-pregnenolone derivatives were prepared via 2-butyl-1,1,3,3-tetramethylguanidine (n-Bu-TMG) catalysed aza-Michael addition of 16-dehydropregnenolone (16-DHP) carried out in [bmim][BF4]. The application of the guanidine base and the imidazolium ionic liquid made it possible to recycle not only the catalyst/solvent mixture but also the excess of the N-heterocyclic reagent. By the introduction of CO2 at the end of the reaction, both the guanidine base and the unreacted (excess) reagent could be converted into ionic species that remained dissolved in the ionic liquid phase, while the steroid components were extracted with an apolar solvent. After the removal of CO2, the experiment could be repeated by the addition of the steroid substrate and only an equimolar amount of the N-heterocycle. The methodology was successfully applied to a number of N-heterocycles, such as imidazole, pyrazole, 1,2,3- and 1,2,4-triazoles, and benzimidazole. Indazole and indole could also be converted into the corresponding products, but a stronger base had to be used to obtain a recyclable system.

Kinetic study of the reaction of thiophene-tocopherols with peroxyl radicals enlightenings the role of O˙⋯S noncovalent interactions in H-atom transfer.

Three new α-tocopherol thiophene derivatives were efficiently synthesized, characterized and used for the first time as chain-breaking antioxidants for the inhibition of the autoxidation of reference oxidizable substrates. The rate constant of the reaction with alkylperoxyl (ROO˙) radicals and the stoichiometry of radical trapping (n) for the thiophene-tocopherol compounds were determined by measuring the oxygen consumption during the autoxidation of styrene or isopropylbenzene, using a differential pressure transducer. The measurement of the reaction with ROO˙ radicals in an apolar solvent at 30 °C showed inhibition rate constants (kinh) in the order of 104 M-1 s-1. To rationalise the kinetic results, the effect of the thiophene ring on the H-atom donation by O-H groups of the functionalized tocopherols was investigated by theoretical calculations. The importance of noncovalent interactions (including an unusual O˙⋯S bond) for the stability of the conformers has been shown, and the O-H bond dissociation enthalpy (BDE(OH)) of these derivatives was determined. Finally, the photophysical properties of these new compounds were investigated to understand if the addition of thiophene groups changes the absorption or emission spectra of the tocopherol skeleton for their possible application as luminescent molecular probes.

Solvation controlled excited-state dynamics in a donor-acceptor phenazine-imidazole derivative.

In the past few decades, significant efforts have been devoted to developing phenazine derivatives in various fields such as medicine, pesticides, dyes, and conductive materials owing to their highly Stokes-shifted fluorescence and distinctive photophysical properties. The modulation of the surrounding environment can effectively influence the luminescent behavior of phenazine derivatives, prompting us to investigate the solvent effect on the excited state dynamics. Herein, we present the solvent controlled excited state dynamics of a novel triphenylamine-based phenazine-imidazole molecule (TPAIP) through steady-state spectra and femtosecond transient absorption spectra. The fluorescence emission spectrum exhibited a redshift with increasing solvent polarity, indicating the existence of a charge transfer state. Furthermore, by tracking the femtosecond transient absorption spectra of TPAIP, we found that the nature of the relaxed S1 state was strongly influenced by the solvent polarity: intersystem crossing character appears in apolar solvent, whereas intramolecular charge transfer character occurs in polar solvent because of solvation. These findings provide significant theoretical insights into the impact of solvents on the excited state dynamics within phenazine derivatives. This understanding supports diverse applications ranging from advanced biological probe design to photocatalysis and pharmaceutical research.

Nanoscale assembly of enantiomeric supramolecular gels driven by the nature of solvents.

Understanding the key parameters that control the self-assembly process is critical to predict self-assembly modes in multi-component systems, which will lead to the development of nanofibrous materials with tuneable properties. Enantiomeric amino acid-based low-molecular-weight gelators (LMWGs) were mixed in polar (polar protic) and aromatic apolar (aromatic) solvents and compared to their individual counterparts to probe the effect of solvent polarity on the self-assembly process. Scanning electron microscopy (SEM) reveals that xerogels of individual components display hollow needles in polar protic solvents, while chiral coils are observed in aromatic solvents. In contrast, the multi-component gel displays hollow needle morphologies in both solvents, indicating similar morphologies in polar protic solvents but an entirely different nanostructure for the individual gel networks in aromatic solvents. PXRD experiments performed on the dried gels showed that the nature of the solvents plays a vital role in the co-assembly process of multi-component gels. The self-assembly modes and the gel state structure of the gels are analysed by wide-angle X-ray diffraction (WAXS) and small-angle neutron diffraction (SANS), which reveals that the mixed gel undergoes different co-assembly modes depending on the nature of the solvent systems. This study shows that different co-assembly modes can be achieved for structurally similar components by varying the solvent polarity, demonstrating the importance of solvent choice in the self-assembly process of multi-component gels.

Solvent–base mismatch enables the deconstruction of epoxy polymers and bisphenol A recovery

The use of an alkaline base mismatched with an apolar aromatic solvent provides a new route to disassemble thermoset epoxy resins resulting in the recovery of the polymer building block bisphenol A.

On the third-order nonlinear optical responses of cis and trans stilbenes - a quantum chemistry investigation.

The second hyperpolarizabilities (γ) of the stilbene molecular switch in its trans and cis forms have been calculated using quantum chemistry methods to address their third-order nonlinear optical contrasts, to assess the reliability of lower-cost DFT methods, and to make comparisons with experiments. First, the reference CCSD(T) method shows that trans-stilbene presents a γ‖ value twice larger than its cis isomer (its γTHS value is 2.7 times larger). Among more cost-effective methods, reliable results are obtained at MP2 as well as with DFT, provided the CAM-B3LYP or ωB97X-D XCFs are employed. Supplementary DFT calculations have investigated the relationships between the accuracy of the exchange-correlation functionals, the fulfillment of Koopmans' theorem, and the delocalization error, and they demonstrated that satisfying Koopmans' theorem is not the condition for the best accuracy but that functionals with small delocalization errors are generally efficient. Using the selected CAM-B3LYP, large γ enhancements by about 70% (trans-stilbene) and 50% (cis-stilbene) have been evidenced when accounting for solvent effects using an implicit solvation model (IEFPCM), even for apolar solvents. Then, the frequency dispersion of the γ responses has been described using Bishop polynomial expansions, allowing comparisons with a broad set of experimental data. To a certain extent, no systematic agreement between the calculations and the measured values was found. On the one hand, the agreement is satisfactory for the γ(-ω;ω,-ω,ω) quantities, provided that the dominant vibrational contribution is taken into account. On the other hand, the agreement is poor for the γ(-2ω;ω,ω,0) and γ(-3ω;ω,ω,ω) quantities, while some inconsistencies between experimental values are also highlighted.

Conformations of Macrocyclic Peptides Sampled by Nuclear Magnetic Resonance: Models for Cell-Permeability.

The biological activities and pharmacological properties of peptides and peptide mimetics are determined by their conformational states. Therefore, a detailed understanding of the conformational landscape is crucial for rational drug design. Nuclear magnetic resonance (NMR) is the only method for structure determination in solution. However, it remains challenging to determine the structures of peptides using NMR because of very weak nuclear Overhauser effects (NOEs), the semiquantitative nature of the rotating frame Overhauser effect (ROE), and the low number of NOEs/ROEs in N-methylated peptides. In this study, we introduce a new approach to investigating the structures of modified macrocyclic peptides. We utilize exact NOEs (eNOEs) in viscous solvent mixtures to replicate various cellular environments. eNOEs provide detailed structural information for highly dynamic modified peptides. Structures of high precision were obtained for cyclosporin A, with a backbone atom rmsd of 0.10 Å. Distinct conformational states in different environments were identified for omphalotin A (OmphA), a fungal nematotoxic and multiple backbone N-methylated macrocyclic peptides. A model for cell-permeation is presented for OmphA, based on its structures in polar, apolar, and mixed polarity solvents. During the transition from a polar to an apolar environment, OmphA undergoes a rearrangement of its H-bonding network, accompanied by a cis to trans isomerization of the ω torsion angle within a type VIa β-turn. We hypothesize that the kinetics of these conformational transitions play a crucial role in determining the membrane-permeation capabilities of OmphA.

Nopadiene: A Pinene-Derived Cyclic Diene as a Styrene Substitute for Fully Biobased Thermoplastic Elastomers.

The bicyclic 1,2-substituted, 1,3-diene monomer nopadiene (1R,5S)-2-ethenyl-6,6-dimethylbicyclo[3.1.1]hept-2-ene was successfully polymerized by anionic and catalytic polymerization. Nopadiene is produced either through a facile one-step synthesis from myrtenal via Wittig-olefination or via a scalable two-step reaction from nopol (10-hydroxymethylene-2-pinene). Both terpenoids originate from the renewable β-pinene. The living anionic polymerization of nopadiene in apolar and polar solvents at 25 °C using organolithium initiators resulted in homopolymers with well-controlled molar masses in the range of 5.6-103.4 kg·mol-1 (SEC, PS calibration) and low dispersities (Đ) between 1.06 and 1.18. By means of catalytic polymerization with Me4CpSi(Me)2NtBuTiCl2 and (Flu)(Pyr)CH2Lu(CH2TMS)2(THF), the 1,4 and 3,4- microstructures of nopadiene are accessible in excellent selectivity. In pronounced contrast to other 1,3-dienes, the rigid polymers of the sterically demanding nopadiene showed an elevated glass temperature, Tg,∞ = 160 °C (in the limit of very high molar mass, Mn). ABA triblock copolymers with a central polymyrcene block and myrcene content of 60-75 mol %, with molar masses of 100-200 kg/mol were prepared by living anionic polymerization of the pinene-derivable monomers nopadiene and myrcene. This diene copolymerization resulted in thermoplastic elastomers displaying nanophase separation at different molar ratios (DSC, SAXS) and an upper service temperature about 30 K higher than that for traditional petroleum-derived styrenic thermoplastic elastomers due to the high glass temperature of polynopadiene. The materials showed good thermal stability at elevated temperatures under nitrogen (TGA), promising tensile strength and ultimate elongation of up to 1600%.