Pyrene Excimer Research Articles

Conformational dynamics of the pyrene excimer.

The conformational dynamics of the pyrene excimer play a critical role in its unique fluorescence properties. Yet, the influence of multiple local minima on its excited-state behavior remains underexplored. Using a combination of time-dependent density functional theory (TD-DFT) and unsupervised machine learning analysis, we have identified and characterized a diverse set of stable excimer geometries in the first excited state. Our analysis reveals that rapid structural reorganization towards the most stable stacked-twisted conformer dominates the excimer's photophysics, outcompeting radiative relaxation. This conformer, which is primarily responsible for the characteristic red-shifted, structureless fluorescence emission, reconciles experimental observations of long fluorescence lifetimes and emission profiles. These findings provide new insights into the excited-state dynamics of excimers. They may inform the design of excimer-based materials in fields ranging from organic electronics to molecular sensing.

Pyrene Based Schiff Base for Cascade Fluorescent "On-Off" Detection of Aluminium(III) and Fluoride Ions and its Applications in Live Cells Imaging.

An easy-to-prepare pyrene-based Schiff base PNZ was synthesized by condensing equimolar amount of 1-pyrenebutyric hydrazide with 2-hydroxy-naphthaldehyde, and employed as a fluorescent chemosensor for in-situ cascade detection of aluminium (Al3+) and fluoride (F-) ions. In DMSO:H2O (1 : 1, v/v), the weakly emissive PNZ showed a significant fluorescence enhancement at 455 nm selectively upon the addition of Al3+ due to the complexation-induced formation of a pyrene excimer. Schiff base PNZ and Al3+ formed a complex in 2 : 1 binding ratio with the estimated binding constants of K1:1=9826.01 M-1 and K2:1=3188.49 M-1. The sensing mechanism was explored by performing quantum mechanical calculations and 1H-NMR titration of PNZ with Al3+. The in-situ formed PNZ-Al3+ complex species enabled the fluorescent turn-off detection of F-. Using PNZ and PNZ-Al3+, the concentrations of Al3+ and F- ions can be detected down to 2.89×10-7 M and 1.88×10-7 M, respectively. The cytotoxicity of the PNZ and its ability to bioimage Al3+ and F- ions was examined in the human cervical cancer cell line. Finally, the receptor PNZ was applied for the quantification of Al3+ and F- ions in various real samples, such as tap water, river water, rainwater, mouthwash, and toothpaste.

Lighting Up Bispyrene‐Functionalized Chiral Molecular Muscles with Switchable Circularly Polarized Excimer Emissions

AbstractAiming at the further extension of the application scope of traditional molecular muscles, a novel bispyrene‐functionalized chiral molecular [c2]daisy chain was designed and synthesized. Taking advantage of the unique dimeric interlocked structure of molecular [c2]daisy chain, the resultant chiral molecular muscle emits strong circularly polarized luminescence (CPL) attributed to the pyrene excimer with a high dissymmetry factor (glum) value of 0.010. More importantly, along with the solvent‐ or anion‐ induced motions of the chiral molecular muscle, the precise regulation of the pyrene stacking within its skeleton results in the switching towards either “inversed” state with sign inversion and larger glum values or “down” state with maintained handedness and smaller glum values, making it a novel multistate CPL switch. As the first example of chiral molecular muscle‐based CPL switch, this proof‐of‐concept study not only successfully widens the application scopes of molecular muscles, but also provides a promising platform for the construction of novel smart chiral luminescent materials for practical applications.

Polymer organic framework-based ratiometric fluorescent probe for non-enzymatic glucose detection

Fluorescent pyrene-based polymer organic frameworks (POFs) PY-POFs were designed and synthesized by a facile solvothermal route for glucose detection, employing melamine, aromatic dialdehydes, 1-pyrenecarboxaldehyde, and phenylboronic acid as building blocks. The structure and photophysical properties of as-prepared POFs were systematically characterized via Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, N2 adsorption isotherms and fluorescence spectroscopy. The PY-POFs possessed intrinsic microporosity derived from extensively interlinked aminal structures, boasting specific surface areas reaching 192 m²/g, pore volumes extending to 0.8079 cm³/g, pore diameters of up to 17 nm, and an average particle dimension of ∼ 31 nm. In addition, the PY-POFs exhibited a dual-wavelength emission of pyrene excimer (λem = 472 nm) and monomer (λem = 382, 400, and 422 nm). When exposed to glucose, the former emission decreased while the latter increased, corresponding to the conformational transition of pyrene molecule from excimer to monomer. The non-enzymatic ratiometric fluorescent sensor displayed remarkable sensitivity towards glucose within 10−200 μM range, with a limit of detection (LOD) of 5.6 µM. Moreover, the glucose detection ability of PY-POFs was also in vivo demonstrated within zebrafish. Application of this sensor to real samples such as human saliva and DMEM biological matrix presented satisfactory results and good reproducibility. These results indicate that the fluorescent glucose sensor PY-POFs have broader prospects for utilization within biological studies.

Advantages of Pyrene Excimer Formation (PEF) over Fluorescence Resonance Energy Transfer (FRET) for Probing the Conformation of Macromolecules in Solution

Advantages of Pyrene Excimer Formation (PEF) over Fluorescence Resonance Energy Transfer (FRET) for Probing the Conformation of Macromolecules in Solution

Optical Monitoring of Supramolecular Interactions in Polymers.

Many stimuli-responsive materials harness the reversible association of supramolecular binding motifs to enable advanced functionalities such as self-healing, switchable adhesion, or mechanical adaptation. Despite extensive research into the structure-property relationships of these materials, direct correlations between molecular-level changes in supramolecular binding and macroscopic material behaviors have mostly remained elusive. Here, we show that this challenge can be overcome with supramolecular binding motifs featuring integrated binding indicators. We demonstrate this using a novel motif that combines a hydrogen-bonding ureido-4-pyrimidinone (UPy) with two strategically placed pyrene fluorophores. Dimerization of this motif promotes pyrene excimer formation, facilitating the straightforward optical quantification of supramolecular assembly under various conditions. We exploit the new motif as a supramolecular cross-linker in poly(methyl acrylate)s to probe the extent of (dis)assembly as a function of cross-linker content, processing history, and applied stimuli. We demonstrate that the stimuli-induced dissociation of hydrogen-bonding linkages strongly depends on the initial cross-link density, which also dictates whether the force-induced dissociation in polymer films correlates with the applied stress or strain. Thus, beyond introducing a robust tool for the in situ study of dynamic (dis)assembly mechanisms in supramolecular systems, our findings provide new insights into the mechanoresponsive behavior of such materials.

Optical Monitoring of Supramolecular Interactions in Polymers

AbstractMany stimuli‐responsive materials harness the reversible association of supramolecular binding motifs to enable advanced functionalities such as self‐healing, switchable adhesion, or mechanical adaptation. Despite extensive research into the structure–property relationships of these materials, direct correlations between molecular‐level changes in supramolecular binding and macroscopic material behaviors have mostly remained elusive. Here, we show that this challenge can be overcome with supramolecular binding motifs featuring integrated binding indicators. We demonstrate this using a novel motif that combines a hydrogen‐bonding ureido‐4‐pyrimidinone (UPy) with two strategically placed pyrene fluorophores. Dimerization of this motif promotes pyrene excimer formation, facilitating the straightforward optical quantification of supramolecular assembly under various conditions. We exploit the new motif as a supramolecular cross‐linker in poly(methyl acrylate)s to probe the extent of (dis)assembly as a function of cross‐linker content, processing history, and applied stimuli. We demonstrate that the stimuli‐induced dissociation of hydrogen‐bonding linkages strongly depends on the initial cross‐link density, which also dictates whether the force‐induced dissociation in polymer films correlates with the applied stress or strain. Thus, beyond introducing a robust tool for the in situ study of dynamic (dis)assembly mechanisms in supramolecular systems, our findings provide new insights into the mechanoresponsive behavior of such materials.

Flexibility of Poly(alkyl methacrylate)s Characterized by Their Persistence Length Determined through Pyrene Excimer Formation.

A series of poly(alkyl methacrylate)s and poly(oligo(ethylene glycol) methyl ether methacrylate)s labeled with 1-pyrenebutanol were referred to as the PyC4-PCnMA samples with n = 1, 4, 6, 8, 12, and 18 and the PyC4-PEGnMA samples with n = 0-5, 9, 16, and 19, respectively. Pyrene excimer formation (PEF) upon the encounter between an excited and a ground-state pyrenyl labels was employed to determine their persistence length (lp) in o-xylene. The fluorescence decays of the PyC4-PCnMA and PyC4-PEGnMA samples were acquired and analyzed with the fluorescence blob model to yield the number (Nblob) of structural units in the volume probed by an excited pyrenyl label. Nblob was found to decrease with an increasing number (NS) of non-hydrogen atoms in the side chain, reaching a plateau for the PyC4-PEGnMA samples with a longer side chain (n = 16 and 19). The Nblob values were used to determine lp. The lp values for the PyC4-PCnMA and PyC4-PEGnMA samples increased linearly with increasing NS2 as predicted theoretically, which agreed with the lp values obtained by viscometry for a series of PCnMA samples. The good agreement between the lp values retrieved by PEF and viscometry served to validate the PEF-based methodology for determining lp for linear polymers.

In situ monitoring of polymeric patchy micelles upon non-covalent post-assembly modification

ABSTRACT Polymeric patchy micelles (PPMs) are nanostructures with distinct regions on their surfaces, offering unique properties for various applications. Herein, we present a straightforward method for monitoring the structure of PPMs formed via non-covalent post-assembly modification (NCPAM). By employing 1-pyrenemethylamine, a pyrene-based molecule, as both a modifier and fluorescent probe, we demonstrate that the formation of PPMs with a higher order aggregation state of pyrene induces a stronger pyrene excimer emission. This leads to variations in the excimer-to-monomer emission ratio, serving as a parameter for studying structural changes in PPMs during NCPAM. In situ monitoring of PPM formation and temperature-dependent transformations is achieved using fluorescent analytical method, providing valuable insights into their structural evolution and dynamic behaviour. This study offers a straightforward approach to understanding and controlling PPM structures, facilitating the design of advanced nanomaterials for diverse applications.

Intermolecular π-π interactions-induced aggregation based on bispyrene for ultrasensitive detection of picric acid (PA) and 2,4-dinitrophenol (DNP)

It was still important to explore excimer emission-based fluorescence probes for nitroaromatics detection by formation or destruction of pyrene excimer with strong emission change. In this work, we have synthesized a simple bis(pyrene) derivative (BisPyH) and studied its optical behavior by using UV–vis and fluorescent spectroscopy. In pure DMSO solution, it emitted a weak blue fluorescence due to the formation of excimer states, on the contrary, the BisPyH in the DMSO/H2O (v/v, 1:1) mixture solution was self-assembled to form aggregates via intermolecular π-π interactions among pyrene units, giving almost 10-fold fluorescence enhancement compared to that in pure DMSO solution. The formed aggregates just offered a perfect platform for the selective detection PA and DNP explosives by quenching the bright green intermolecular-excimer emission in competitive environment. BisPyH exhibited a limit of detection (LOD) towards PA, and DNP as low as 7.32 × 10−8, and 8.11 × 10−8 M, respectively. Subsequently, the fluorescence quenching mechanism was demonstrated by the density functional theory (DFT), UV–vis and fluorescence spectra, SEM, and the quenching constants. Furthermore, filter paper strips and thin-layer chromatography (TLC) plates coated with BisPyH were able to detect PA and DNP in the practical application.

Pyrene excimer-based fluorescent chemosensor for cascade detection of Zn(II) and phosphate ions and its applications

There is growing research on developing fluorescent chemosensors that can detect multiple analytes. Herein, a pyrene-naphthaldehyde based Schiff base PNY was synthesized, characterized, and employed for the cascade fluorescent ‘Off-On-Off’ detection of Zn2+ and phosphate ions. The interaction of PNY with Zn2+ led to a distinct fluorescence enhancement at 450 nm, and the fluorescent color of PNY was changed from blue to cyan-blue due to the complexation-induced formation of a pyrene excimer. PNY, as a fluorescent turn-on sensor can be employed to detect Zn2+ down to 2.20 × 10−7 M. Subsequently, the in-situ formed PNY-Zn2+ complex gets decomplex upon the addition of phosphate ion among other tested anions with a detection limit of 3.42 × 10−7 M. With the addition of phosphate ion, fluorescence intensity of PNY-Zn2+ at 450 nm was quenched with the concomitant formation of an emission peak at around 396 nm. The excimer-monomer mechanism was used to explain the sensing ability of PNY. Further, to complement the phosphate ion selectivity, the ability of PNY-Zn2+ to detect adenosine triphosphate (ATP) was explored. At last, the analytical novelty of PNY and PNY-Zn2+ was explored by quantifying Zn2+ and phosphate ions in real environmental and biological samples.

Design and synthesis of pyrene-based probes and their fluorescent detection of Sb(III)

A series of pyrene-based fluorescent (FL) probes for Sb(III) were designed and synthesized. All of them exhibited luminescence by pyrene excimers in the mixture of DMSO and water and showed enhanced emission with the addition of Sb(III). By comparing their FL response to Sb(III), the effects of intramolecular hydrogen bond, inductive effect, and steric effect were investigated. Meanwhile, the FL enhancement factor of the best performing probe reached 10.28 and the detection limit was calculated to be 0.0535 mg/L, indicating that it might be used as a potential candidate for the treatment of Sb(III) in printing and dyeing wastewater.

Accurate Determination of the Average Rate Constant of Pyrene Excimer Formation for Pyrene-Labeled Macromolecules from the Analysis of Individual Fluorescence Decays with Sums of Exponentials.

The average rate constant (⟨k⟩) for pyrene excimer formation (PEF) between an excited and a ground-state pyrenyl label covalently attached to a pyrene-labeled macromolecule (PyLM) has been found to be an ideal parameter to probe macromolecular conformations due to its proportionality to the local concentration ([Py]loc) of pyrenyl labels in PyLM. To date, ⟨k⟩ has only been determined with the model-free analysis (MFA) involving the global analysis of the pyrene monomer and excimer fluorescence decays of PyLM. Unfortunately, the MFA is computationally demanding which prevents its widespread use. To circumvent this complication, a methodology is introduced that involves the analysis of individual fluorescence decays with sums of exponentials (SoE), which are commonly used in the analysis packages of commercial time-resolved fluorometers. The individual fluorescence decays of the pyrene monomer acquired with 286 PyLM were analyzed with a SoE to yield ⟨kSoE-M⟩. The strong correlation between ⟨kSoE-M⟩ and ⟨kMF⟩ obtained from the global MFA indicated that ⟨kSoE-M⟩ was a good representation of ⟨k⟩. Furthermore, the AE-/AE+ ratio, equal to the ratio of the sum of the negative pre-exponential factors over the sum of the positive pre-exponential factors, was determined by fitting the individual pyrene excimer fluorescence decays of the 286 PyLM with a SoE. AE-/AE+ was found to take a value between -1.0 and -0.8, indicating that the pyrenyl labels were not aggregated. This result indicated that [Py]loc was well described by ⟨kSoE-M⟩, so that ⟨kSoE-M⟩ could be used to describe the conformation of macromolecules in the same manner as ⟨kMF⟩. Consequently, the methodology based on the analysis of individual fluorescence decays with sums of exponentials to determine ⟨kSoE-M⟩ and AE-/AE+ provides a robust alternative to the use of the MFA for the study of PyLM to many scientists interested in the characterization of macromolecular conformations.

Eclipsed and Twisted Excimers of Pyrene and 2-Azapyrene: How Nitrogen Substitution Impacts Excimer Emission.

Due to their unique photophysical and electronic properties, pyrene and its analogues have been the subject of extensive research in recent decades. The propensity of pyrene and its derivatives to form excimers has found wide application in various fields. Nitrogen-substituted pyrene derivatives display similar photophysical properties, but for them, excimer emission has not been reported to date. Here, we use time-dependent density functional theory (TD-DFT) calculations to investigate the low-lying exciton states of dimers of pyrene and 2-azapyrene. The excimer equilibrium structures are determined and the contribution of charge transfer (CT) excitations and intermolecular interactions to the exciton states is disclosed using a diabatization procedure. The study reveals that the dimers formed by the two molecules have quite similar exciton-state patterns, in which the relevant CT contributions govern the formation of excimer states, along with the La/Lb state inversion. In contrast with pyrene, the dipole-dipole interactions in 2-azapyrene stabilize the dark eclipsed excimer structure and increase the barrier for conversion into a bright twisted excimer. It is suggested that these differences in the nitrogen-substituted derivative might influence the excimer emission properties.

Investigation of silica particle growth by incorporation of a pyrene fluorescent probe

The growth of silica particles synthesized by the Stöber method was investigated by the co-condensation of pyrene sulfonyl chloride (PySCl) coupled to (3-aminopropyl)triethoxysilane (APTES). Growth by monomer addition could be distinguished from growth by aggregation based on the intensity of the pyrene excimer emission of the resulting particles. The influence of the base concentration, water/ethanol ratio, solvent, temperature, and type of silica precursor was studied. At high hydrolysis rates, the growth occurred primarily by aggregation, whereas growth by monomer addition was predominant at low hydrolysis rates. The results were confirmed by evaluating the accessibility of the co-condensed pyrene moieties and by determining the porosity of the particles.

Pyrene monomer-excimer dynamics to reveal molecular organization in mesoporous hybrid silica films.

Self-assembly and characteristics of hybrid mesoporous silica film templates remain a subject of inquiry. The short time scale of the inorganic condensation and formation of micelles makes our understanding of this process insufficient. To provide an insight into the evaporation-induced self-assembly of such films, we synthesized an efficient molecular probe of the triethoxysilane precursor bearing a pyrene derivative. The probe was introduced into the porous film at the synthesis stage through the sol-gel co-condensation method. At different synthesis stages, the emission of pyrene moieties was measured by fluorescence spectroscopy, revealing the placement of probes within the film. We also report dynamic excimer formation upon template removal. Moreover, we evaluate the influence of several parameters on the pyrene excimer formation phenomenon. The pore geometry, probe concentration, and the presence of another organosilane precursor are investigated in this work.

Engineering circularly polarized light emission in nanostructured oligodimethylsiloxane-helicene chiral materials.

Chiroptical properties in the bulk state can be tuned by controlling the formation of chiral ordered nanostructures. Here, we present a series of discrete oligodimethylsiloxane-helicene-pyrene block molecules with varying oDMS lengths and study the nanostructures formed in both bulk and solution, including their chiroptical properties. In bulk, ordered 2D nanostructures self-assemble, driven by phase segregation induced by the siloxane oligomers, with clear differences in the properties of the racemic and enantiopure versions. Moreover, intermolecular pyrene interactions lead to excimer emission. As a result, up to a 5-fold increase in circularly polarized luminescence is observed in the solid state as compared to the solution, accompanied by a clear influence of the pyrene excimer emission on the overall emission process. Interestingly, in the ordered lamellar packing achieved from long oDMS units, the excimer emission shows very little net circular polarization, while in the disordered state achieved from shorter oDMS units, this excimer emission displays a significant degree of circular polarization. These results demonstrate that functionalizing chiroptical building blocks with discrete oligodimethylsiloxane chains is a versatile strategy to control photophysical properties and modulate chiroptical emission in bulk. This approach advances the integration of chiroptical materials into devices, enabling diverse applications ranging from optoelectronics to communication technologies.

Interfacial self-assembly of a chiral pyrene exciplex into a superhelix with enhanced circularly polarized luminescence.

We found that the interfacially confined self-assembly of pyrene and phenanthrene glutamides can form strong exciplexes and amorphous superhelices, which show intensity-enhanced and sign-inverted CPL activity with improved quantum yield compared to a pyrene excimer. This work unveils the predominant role of supramolecular nanostructures over molecular configurations on CPL performance.

Tailoring pyrene excimer luminescence via controlled sulfur oxidation

Manipulation of the oxidation degree of sulfur is carried out to synthesize sulfide-, sulfoxide- and sulfone-substituted pyrenes, fine-tune the electronic effect and stiffness of the molecules, and obtain optimal luminous efficiency of the excimers.

Dipeptides Containing Pyrene and Modified Photochemically Reactive Tyrosine: Noncovalent and Covalent Binding to Polynucleotides.

Dipeptides 1 and 2 were synthesized from unnatural amino acids containing pyrene as a fluorescent label and polynucleotide binding unit, and modified tyrosine as a photochemically reactive unit. Photophysical properties of the peptides were investigated by steady-state and time-resolved fluorescence. Both peptides are fluorescent (Φf = 0.3-0.4) and do not show a tendency to form pyrene excimers in the concentration range < 10-5 M, which is important for their application in the fluorescent labeling of polynucleotides. Furthermore, both peptides are photochemically reactive and undergo deamination delivering quinone methides (QMs) (ΦR = 0.01-0.02), as indicated from the preparative photomethanolysis study of the corresponding N-Boc protected derivatives 7 and 8. Both peptides form stable complexes with polynucleotides (log Ka > 6) by noncovalent interactions and similar affinities, binding to minor grooves, preferably to the AT reach regions. Peptide 2 with a longer spacer between the fluorophore and the photo-activable unit undergoes a more efficient deamination reaction, based on the comparison with the N-Boc protected derivatives. Upon light excitation of the complex 2·oligoAT10, the photo-generation of QM initiates the alkylation, which results in the fluorescent labeling of the oligonucleotide. This study demonstrated, as a proof of principle, that small molecules can combine dual forms of fluorescent labeling of polynucleotides, whereby initial addition of the dye rapidly forms a reversible high-affinity noncovalent complex with ds-DNA/RNA, which can be, upon irradiation by light, converted to the irreversible (covalent) form. Such a dual labeling ability of a dye could have many applications in biomedicinal sciences.