Search Results (17)

Nitrogen-fused conjugated heterocycles have attracted growing interest owing to their tunable electronic properties and potential in organic optoelectronics. In this study, two centrosymmetric donor–acceptor-type emitters PP-6F and PPA-3F were designed by incorporating trifluorophenyl and anthracene acceptor units into a pyrrolo[3,2-b]pyrrole (PP) framework. The experimental and theoretical results reveal that subtle modulations in molecular conformation and π-conjugation pathways strongly affect the excited-state characteristics. PP-6F, featuring a nearly coplanar donor–acceptor configuration, exhibits efficient π-electron delocalization and a dominant local excitation (LE) emission with a large oscillator strength. In contrast, the bulky anthracene in PPA-3F increases the donor–acceptor dihedral angle, reduces conjugation coupling, and promotes orbital separation, leading to a hybrid intramolecular charge transfer and local excitation (ICT/LE) excited state. The rigid anthracene framework suppresses structural reorganization and nonradiative decay, allowing PPA-3F to retain a relatively high oscillator strength despite its charge-transfer nature. This work demonstrates that fine-tuning donor–acceptor dihedral angles and conjugation continuity within PP-based systems is an effective strategy for balancing LE and ICT emissions and developing high-efficiency nitrogen-fused organic emitters and scintillators. Full article

BOPAM exhibits high fluorescence quantum yields, along with exceptional photostability, rendering it a promising platform for applications as fluorescence sensors. However, the development of BOPAM-based fluorophores with extended emission wavelengths remains limited, and the underlying mechanisms of fluorescence quenching via the population of dark twisted intramolecular charge transfer (¹TICT) excited states are not yet fully understood. To address these gaps, we synthesized a series of BOPAM derivatives by incorporating electron-donating groups at the boron atoms and the phenyl rings of the BOPAM core. The introduction of bromide, phenyl, and naphthyl groups preserved the intrinsic locally excited (¹LE) emission of BOPAM. In contrast, the incorporation of diphenylamine (BP-DA) and triphenylamine (BP-TA) moieties resulted in a red-shifted emission, attributed to an enhanced intramolecular charge transfer (ICT) process. Notably, in acetonitrile, BP-DA exhibited weak fluorescence originating from a ¹TICT state, which was populated via the S₂ → ¹TICT transition. Furthermore, the emission observed from BP-TA was associated with a higher-lying excited state, likely the initially populated S₂ state possessing a ¹LE character. These findings not only introduce novel red-emissive BOPAM-based fluorophores, but also offer valuable insights into the role of the S₂ state in governing fluorescence quenching mechanisms in BOPAM derivatives. Full article

β-galactosidase (β-Gal) has emerged as a pivotal biomarker for the comprehensive investigation of diseases associated with cellular senescence. The development of a fluorescent sensor is of considerable importance for precisely detecting the activity and spatial distribution of β-Gal. In this study, we developed two excited-state-altering responsive fluorescent sensors (TF1 and TF2) for ratiometric detection of β-Gal. Two TCF dyes, composed of tricyanofuran (TCF) and naphthol units, feature electron “pull–push” systems and are quenched fluorescence by β-Gal. Upon β-Gal hydrolysis, a significant ratiometric shift in absorption from ca. 475 nm to 630 nm is observed, accompanied by the emergence of a fluorescence signal at ca. 660 nm. The enzyme-responsive optical red-shifts are attributed to the excited-state transition from intramolecular charge transfer (ICT) state to local excited (LE) state, which was confirmed by density functional theory (DFT) calculations. Both fluorescent sensors display exceptional sensitivity and selectivity for the response of β-Gal in PBS solution and are capable of tracking β-Gal within senescent A549 cells. This study introduces a framework for developing multimodal optical probes by systematically modulating excited-state properties, demonstrating their utility in senescence studies, diagnostic assay design, and therapeutic assessment. Full article

Poly-CPDTBT, as typical low-band gap copolymers, have potential applications in organic bulk heterojunction solar cells. To have a clear picture of its excited-state processes, the first task is to understand their excited states, in particular, electronic character and relevant optical absorption. Herein, the low-lying singlet excited states of Poly-CPDTBT oligomers were investigated via Algebraic Diagrammatic Construction Second Order (ADC(2)) and time-dependent density functional theory (TDDFT) method with several functionals. Six CPDTBT_N (N = 1–6) oligomers were taken as prototypes to study their excited states in detail. The results provide interesting clues to extrapolate the photophysical properties of such polymers with potential applications in photovoltaic materials. The result provided by ωB97XD functional gives good agreement with the experiment result. The vertical excitation energies of the four lowest excited states decrease almost linearly with increasing polymerization degree (N) for CPDTBT_N (N = 1–6). The transition density analysis indicates that the local excitations (LE) and the short-distance charge transfer (CT) excitations between two adjacent CPDT and BT units are dominant for low-lying excited states for short oligomers. For the long-chain oligomers (trimer to hexamer), the transition density shows a ladder (or zigzag) pattern along the diagonal blocks at the planar geometry. For long oligomers, the whole chain is involved in the transitions, and the CT excitations only exist between two adjacent CPDT and BT units. The present work provides a valuable basis for understanding the excited-state processes of Poly-CPDTBT and other conjugated polymers that conduct solar energy conversions, which has great significance for the development of new solar cells. Full article

Chemical structures bearing a combination of aggregation-induced emission enhancement (AIEE) and intramolecular charge transfer (ICT) properties attracted the attention of many researchers. Recently, there is an increasing demand to pose tunable AIEE and ICT fluorophores that could present their conformation changes-related emission colors by adjusting the medium polarity. In this study, we designed and synthesized a series of 4-alkoxyphenyl-substituted 1,8-naphthalic anhydride derivatives NAxC using the Suzuki coupling reaction to construct donor–acceptor (D-A)-type fluorophores with alkoxyl substituents of varying carbon chain lengths (x = 1, 2, 4, 6, 12 in NAxC). To explain the observation that molecules with longer carbon chains revealed unusual fluorescence enhancement in water, we study the optical properties and evaluate their locally excited (LE) and ICT states by solvent effects combined with Lippert–Mataga plots. Then, we explored the self-assembly abilities of these molecules in water-organic (W/O) mixed solutions and observed the morphology of its nanostructure using a fluorescence microscope and SEM. The results show that NAxC, x = 4, 6, 12 show different degrees of self-assembly behaviors and corresponding aggregation-induced emission enhancement (AIEE) progresses. At the same time, different nanostructures and corresponding spectral changes can be obtained by adjusting the water ratio in the mixed solution. That is, NAxC compounds present different transitions between LE, ICT and AIEE based on the polarity, water ratio and time changes. We designed NAxC as the structure–activity relationship (SAR) of the surfactant to demonstrate that AIEE comes from the formation of micelle-like nanoaggregates, which causes a restriction of the transfer from the LE state to the ICT state, and micelle formation results in a blue-shift in emission and enhances the intensity in the aggregate state. Among them, NA12C is most likely to form micelles and the most obvious fluorescence enhancement, which will switch over time due to the nano-aggregation transition. Full article

Intermolecular interactions modulate the electro-optical properties of molecular materials and the nature of low-lying exciton states. Molecular materials composed by oligoacenes are extensively investigated for their semiconducting and optoelectronic properties. Here, we analyze the exciton states derived from time-dependent density functional theory (TDDFT) calculations for two oligoacene model aggregates: naphthalene and anthracene dimers. To unravel the role of inter-molecular interactions, a set of diabatic states is selected, chosen to coincide with local (LE) and charge-transfer (CT) excitations within a restricted orbital space including two occupied and two unoccupied orbitals for each molecular monomer. We study energy profiles and disentangle inter-state couplings to disclose the (CT) character of singlet and triplet exciton states and assess the influence of inter-molecular orientation by displacing one molecule with respect to the other along the longitudinal translation coordinate. The analysis shows that (CT) contributions are relevant, although comparably less effective for triplet excitons, and induce a non-negligible mixed character to the low-lying exciton states for eclipsed monomers and for small translational displacements. Such (CT) contributions govern the L_a/L_b state inversion occurring for the low-lying singlet exciton states of naphthalene dimer and contribute to the switch from H- to J-aggregate type of the strongly allowed B_b transition of both oligoacene aggregates. Full article

The efficiency of intramolecular charge transfer (ICT)-based emission on π-aromatic-group-appended closo-ortho-carboranyl luminophores is known to be affected by structural fluctuations and molecular geometry, but investigation of this relationship has been in progress to date. In this study, four naphthyl-based bis-o-carboranyl compounds, in which hydrogen (15CH and 26CH) or trimethysilyl groups (15CS and 26CS) were appended at the o-carborane cage, were synthesized and fully characterized. All the compounds barely displayed an emissive trace in solution at 298 K; however, 15CH and 26CH distinctly exhibited a dual emissive pattern in rigid states (in solution at 77 K and in films), attributed to locally excited (LE) and ICT-based emission, while 15CS and 26CS showed strong ICT-based greenish emission. Intriguingly, the molecular structures of the four compounds, analyzed by single X-ray crystallography, showed that the C-C bond axis of the o-carborane cage in the trimethysilyl group-appended compounds 15CS and 26CS were more orthogonal to the plane of the appended naphthyl group than those in 15CH and 26CH. These features indicate that 15CS and 26CS present an efficient ICT transition based on strong exo-π-interaction, resulting in a higher quantum efficiency (Φ_em) for ICT-based radiative decay than those of 15CH and 26CH. Moreover, the 26CS structure revealed most orthogonal geometry, resulting in the highest Φ_em and lowest k_nr values for the ICT-based emission. Consequently, all the findings verified that efficient ICT-based radiative decay of aromatic group-appended o-carboranyl luminophores could be achieved by the formation of a specific geometry between the o-carborane cage and the aromatic plane. Full article

The modulation of intermolecular interactions upon aggregation induces changes in excited state properties of organic molecules that can be detrimental for some optoelectronic applications but can be exploited for others. The time-dependent density functional theory (TDDFT) is a cost-effective approach to determining the exciton states of molecular aggregates, and it has been shown to provide reliable results when coupled with the appropriate choice of the functional. Here we apply a general procedure to analyze the aggregates’ exciton states derived from TDDFT calculations in terms of diabatic states chosen to coincide with local (LE) and charge-transfer (CT) excitations within a restricted orbital space. We apply the approach to study energy profiles, interstate couplings, and the charge-transfer character of singlet and triplet exciton states of perylene di-imide aggregates (PDI). We focus on the intermolecular displacement along the longitudinal translation coordinate, which mimics different amounts of slip-stacking observed in PDI crystals. The analysis, in terms of symmetry-adapted Frenkel excitations (FE) and charge-resonance (CR) states and their interactions, discloses how the interchange of the H/J character for small longitudinal shifts, previously reported for singlet exciton states, also occurs for triplet excitons. Full article

The nature and mechanisms of interaction between two selected methyl benzoate derivatives (methyl o-methoxy p-methylaminobenzoate–I and methyl o-hydroxy p-methylaminobenzoate–II) and model transport protein bovine serum albumin (BSA) was studied using steady-state and time-resolved spectroscopic techniques. In order to understand the role of Trp residue of BSA in the I-BSA and II-BSA interaction, the effect of free Trp amino acid on the both emission modes (LE–locally excited (I and II) and ESIPT–excited state intramolecular proton transfer (II)) was investigated as well. Experimental results show that the investigated interactions (with both BSA and Trp) are mostly conditioned by the ground and excited state complex formation processes. Both molecules form stable complexes with BSA and Trp (with 1:1 stoichiometry) in the ground and excited states. The binding constants were in the order of 10⁴ M⁻¹. The absorption- and fluorescence-titration experiments along with the time-resolved fluorescence measurements show that the binding of the I and II causes fluorescence quenching of BSA through the static mechanism, revealing a 1:1 interaction. The magnitude and the sign of the thermodynamic parameters, ΔH, ΔS, and ΔG, determined from van’t Hoff relationship, confirm the predominance of the hydrogen-bonding interactions for the binding phenomenon. To improve and complete knowledge of methyl benzoate derivative-protein interactions in relation to supramolecular solvation dynamics, the time-dependent fluorescence Stokes’ shifts, represented by the normalized spectral response function c(t), was studied. Our studies reveal that the solvation dynamics that occurs in subpicosecond time scale in neat solvents of different polarities is slowed down significantly when the organic molecule is transferred to BSA cavity. Full article

We here investigate the Electronic Circular Dichroism (ECD) Spectra of two representative Guanine-rich sequences folded in a Quadruple helix (GQ), by using a recently developed fragment diabatisation based excitonic model (FrDEx). FrDEx can include charge transfer (CT) excited states and consider the effect of the surrounding monomers on the local excitations (LEs). When applied to different structures generated by molecular dynamics simulations on a fragment of the human telomeric sequence (Tel21/22), FrDEx provides spectra fully consistent with the experimental one and in good agreement with that provided by quantum mechanical (QM) method used for its parametrization, i.e., TD-M05-2X. We show that the ECD spectrum is moderately sensitive to the conformation adopted by the bases of the loops and more significantly to the thermal fluctuations of the Guanine tetrads. In particular, we show how changes in the overlap of the tetrads modulate the intensity of the ECD signal. We illustrate how this correlates with changes in the character of the excitonic states at the bottom of the ${\mathrm{L}}_{\mathrm{a}}$ and ${\mathrm{L}}_{\mathrm{b}}$ bands, with larger LE and CT involvement of bases that are more closely stacked. As an additional test, we utilised FrDEx to compute the ECD spectrum of the monomeric and dimeric forms of a GQ forming sequence T30695 (5${}^{\prime }$TGGGTGGGTGGGTGGG3${}^{\prime }$), i.e., a system containing up to 24 Guanine bases, and demonstrated the satisfactory reproduction of the experimental and QM reference results. This study provides new insights on the effects modulating the ECD spectra of GQs and, more generally, further validates FrDEx as an effective tool to predict and assign the spectra of closely stacked multichromophore systems. Full article

Deep blue luminescent materials play a crucial role in the organic light-emitting diodes (OLEDs). In this work, a novel deep blue molecule based on hybridized local and charge-transfer (HLCT) excited state was reported with the emission wavelength of 423 nm. The OLED based on this material achieved high maximum external quantum efficiency (EQE) of 4% with good color purity. The results revealed that the locally-excited (LE)-dominated HLCT excited state had obvious advantages in short wavelength and narrow spectrum emission. What is more, the experimental and theoretical combination was used to describe the excited state characteristic and to understand photophysical property. Full article

The excited state Raman spectra of 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) in the locally-excited (LE) and the intramolecular charge transfer (ICT) states have been separately measured by time-resolved stimulated Raman spectroscopy. In a polar dimethylsulfoxide solution, the ultrafast ICT of DCM with a time constant of 1.0 ps was observed in addition to the vibrational relaxation in the ICT state of 4–7 ps. On the other hand, the energy of the ICT state of DCM becomes higher than that of the LE state in a less polar chloroform solution, where the initially-photoexcited ICT state with the LE state shows the ultrafast internal conversion to the LE state with a time constant of 300 fs. The excited-state Raman spectra of the LE and ICT state of DCM showed several major vibrational modes of DCM in the LE and ICT conformer states coexisting in the excited state. Comparing to the time-dependent density functional theory simulations and the experimental results of similar push-pull type molecules, a twisted geometry of the dimethylamino group is suggested for the structure of DCM in the S₁/ICT state. Full article

The design of improved organic linkers for the further engineering of smarter metal–organic framework (MOF) materials has become a paramount task for a wide number of material scientists. In this report, a luminescent double-functionalized push–pull (electron donor–acceptor) archetype organic molecule, dimethyl 4-amino-8-cyanonaphthalene-2,6-dicarboxylate (Me₂CANADC), has been synthesized and characterized. The optical steady-state properties of Me₂CANADC are strongly influenced by the surrounding environment as a direct consequence of its strong charge transfer (CT) character. The relaxation from its first electronically excited singlet state follows a double pathway: (1) on one side deactivating from its local excited (LE) state in the sub-picosecond or picosecond time domain, and (2) on the other side undergoing an ultrafast intramolecular charge transfer (ICT) reaction that is slowing down in viscous solvents. The deactivation to the ground state of these species with CT character is the origin of the Me₂CANADC luminescence, and they present solvent-dependent lifetime values ranging from 8 to 18 ns. The slow photodynamics of Me₂CANADC unveils the coexistence of a non-emissive triplet excited state and the formation of a long-lived charge separated state (2 µs). These observations highlight the promising optical properties of Me₂CANADC linker, opening a window for the design of new functional MOFs with huge potential to be applied in the fields of luminescent sensing and optoelectronics. Full article

Closo-o-carboranyl compounds bearing the ortho-type perfectly distorted or planar terphenyl rings (closo-DT and closo-PT, respectively) and their nido-derivatives (nido-DT and nido-PT, respectively) were synthesized and fully characterized using multinuclear NMR spectroscopy and elemental analysis. Although the emission spectra of both closo-compounds exhibited intriguing emission patterns in solution at 298 and 77 K, in the film state, closo-DT mainly exhibited a π-π* local excitation (LE)-based emission in the high-energy region, whereas closo-PT produced an intense emission in the low-energy region corresponding to an intramolecular charge transfer (ICT) transition. In particular, the positive solvatochromic effect of closo-PT and theoretical calculation results at the first excited (S₁) optimized structure of both closo-compounds strongly suggest that these dual-emissive bands at the high- and low-energy can be assigned to each π-π* LE and ICT transition. Interestingly, both the nido-compounds, nido-DT and nido-PT, exhibited the only LE-based emission in solution at 298 K due to the anionic character of the nido-o-carborane cages, which cannot cause the ICT transitions. The specific emissive features of nido-compounds indicate that the emissive color of closo-PT in solution at 298 K is completely different from that of nido-PT. As a result, the deboronation of closo-PT upon exposure to increasing concentrations of fluoride anion exhibits a dramatic ratiometric color change from orange to deep blue via turn-off of the ICT-based emission. Consequently, the color change response of the luminescence by the alternation of the intrinsic electronic transitions via deboronation as well as the structural feature of terphenyl rings indicates the potential of the developed closo-o-carboranyl compounds that exhibit the intense ICT-based emission, as naked-eye-detectable chemodosimeters for fluoride ion sensing. Full article

The comprehensive characterization of Intramolecular Charge Transfer (ICT) stemming in push-pull molecules with a delocalized π-system of electrons is noteworthy for a bespoke design of organic materials, spanning widespread applications from photovoltaics to nanomedicine imaging devices. Photo-induced ICT is characterized by structural reorganizations, which allows the molecule to adapt to the new electronic density distribution. Herein, we discuss recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles. We focus the discussion on femtosecond Transient Absorption Spectroscopy (TAS) enabling us to follow the transition from a Locally Excited (LE) state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms. In many cases, the charge transfer transition is accompanied by structural rearrangements, such as the twisting or molecule planarization. The possibility of an accurate prediction of the charge-transfer occurring in complex molecules and molecular materials represents an enormous advantage in guiding new molecular and materials design. We briefly report on recent advances in ultrafast multidimensional spectroscopy, in particular, Two-Dimensional Electronic Spectroscopy (2DES), in unraveling the ICT nature of push-pull molecular systems. A theoretical description at the atomistic level of photo-induced molecular transitions can predict with reasonable accuracy the properties of photoactive molecules. In this framework, the review includes a discussion on the advances from simulation and modeling, which have provided, over the years, significant information on photoexcitation, emission, charge-transport, and decay pathways. Density Functional Theory (DFT) coupled with the Time-Dependent (TD) framework can describe electronic properties and dynamics for a limited system size. More recently, Machine Learning (ML) or deep learning approaches, as well as free-energy simulations containing excited state potentials, can speed up the calculations with transferable accuracy to more complex molecules with extended system size. A perspective on combining ultrafast spectroscopy with molecular simulations is foreseen for optimizing the design of photoactive compounds with tunable properties. Full article