Excited-state Symmetry Breaking Research Articles

Steric Control of Luminescence in Phenyl-Substituted Trityl Radicals.

Triphenylmethyl (trityl) radicals have shown potential for use in organic optoelectronic applications, but the design of practical trityl structures has been limited to donor/radical charge-transfer systems due to the poor luminescence of alternant symmetry hydrocarbons. Here, we circumvent the symmetry-forbidden transition of alternant hydrocarbons via excited-state symmetry breaking in a series of phenyl-substituted tris(2,4,6-trichlorophenyl)methyl (TTM) radicals. We show that 3-fold phenyl substitution enhances the emission of the TTM radical and that steric control modulates the optical properties in these systems. Simple ortho-methylphenyl substitution boosts the photoluminescence quantum efficiency from 1% (for TTM) to 65% at a peak wavelength of 612 nm (for 2-T3TTM) in solution. In the crystalline solid state, the neat 2-T3TTM radical shows a remarkably high photoluminescence quantum efficiency of 25% for emission peaking at 706 nm. This has implications in the design of aryl-substituted radical structures where the electronic coupling of the substituents influences variables such as emission, charge transfer, and spin interaction.

Excited-State Symmetry Breaking in Solvent Mixtures.

A large number of multipolar dyes undergo excited-state symmetry breaking (ESSB) in polar media. During this process, electronic excitation, initially distributed evenly over the molecule, localizes, at least partially, on one donor-acceptor branch. To resolve its initial stage, ESSB is investigated with a donor-acceptor-donor dye in binary mixtures of nonpolar and polar solvents using time-resolved infrared absorption spectroscopy. The presence of a few polar molecules around the dye is sufficient to initiate ESSB. Although the extent of asymmetry in a mixture is close to that in a pure solvent of similar polarity, the dynamics are slower and involve translational diffusion. However, preferential solvation in the mixtures leads to a larger local polarity. Furthermore, inhomogeneous broadening of the S1 ← S0 absorption band of the dye is observed in the mixtures, allowing for a photoselection of solutes with different local environments and ESSB dynamics.

Excited-state symmetry breaking in quadrupolar pull-push-pull molecules: dicyanovinyl vs. cyanophenyl acceptors.

A significant number of quadrupolar dyes behave as their dipolar analogues when photoexcited in polar environments. This is due to the occurrence of excited-state symmetry breaking (ES-SB), upon which the electronic excitation, initially distributed over the whole molecule, localises preferentially on one side. Here, we investigate the ES-SB properties of two A-D-A dyes, consisting of a pyrrolo-pyrrole donor (D) and either cyanophenyl or dicyanovinyl acceptors (A). For this, we use time-resolved vibrational spectroscopy, comparing IR absorption and femtosecond stimulated Raman spectroscopies. Although dicyanovinyl is a stronger electron-withdrawing group, ES-SB is not observed with the dicyanovinyl-based dye even in highly polar media, whereas it already takes place in weakly polar solvents with dyes containing cyanophenyl accepting groups. This difference is attributed to the large electronic coupling between the D-A branches in the former dye, whose loss upon symmetry breaking cannot be counterbalanced by a gain in solvation energy. Comparison with analogues of the cyanophenyl-based dye containing different spacers reveals that interbranch coupling does not so much depend on the distance between the D-A subunits than on the nature of the spacer. We show that transient Raman spectra probe different modes of these centrosymmetric molecules but are consistent with the transient IR data. However, lifetime broadening of the Raman bands, probably due to the resonance enhancement, may limit the application of this technique for monitoring ES-SB.

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

Charge transfer (CT) is key for molecular photonics, governing the optical properties of chromophores comprising electron-rich and electron-deficient components. In photoexcited dyes with an acceptor-donor-acceptor or donor-acceptor-donor architecture, CT breaks their quadrupolar symmetry and yields dipolar structures manifesting pronounced solvatochromism. Herein, we explore the effects of electronic coupling through biaryl linkers on the excited-state symmetry breaking of such hybrid dyes composed of an electron-rich core, i.e., 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP), and pyrene substituents that can act as electron acceptors. Experimental and theoretical studies reveal that strengthening the donor-acceptor electronic coupling decreases the CT rates and the propensity for symmetry breaking. We ascribe this unexpected result to effects of electronic coupling on the CT thermodynamics, which in its turn affects the CT kinetics. In cases of intermediate electronic coupling, the pyrene-DHPP conjugates produce fluorescence spectra, spreading over the whole visible range, that in addition to the broad CT emission, show bands from the radiative deactivation of the locally excited states of the donor and the acceptors. Because the radiative deactivation of the low-lying CT states is distinctly slow, fluorescence from upper locally excited states emerge leading to the observed anti-Kasha behaviour. As a result, these dyes exhibit white fluorescence. In addition to demonstrating the multifaceted nature of the effects of electronic coupling on CT dynamics, these chromophores can act as broad-band light sources with practical importance for imaging and photonics.

Minimal model of excited-state symmetry breaking in symmetric dimers and covalently linked dyads.

A model of symmetry breaking (SB) charge separation in symmetric excited dyads and dimers is presented. The minimal model should include at least four basis electronic states due to a small energy gap between the locally excited and charge separated (zwitterionic) states of the chromophores. There are electronic couplings between all these states. The model includes the following interactions: (i) the Coulomb interaction between charges on the chromophores of the dyad, (ii) the interaction of the dipole moment of the asymmetric dyad with the solvent polarization, and (iii) the electronic-vibrational interaction. SB becomes possible only if the intensity of these interactions exceeds a threshold value. The threshold vanishes if there is a degeneration of the levels. Unusual resonant dependencies of the dissymmetry degree on the model parameters are revealed. Resonances arise due to the degeneration of energy levels. The ranges of the parameters in which energy level crossings occur are established. The oddity lies in the dependence of the resonance shape on the parameters of the model. A variation in the electronic couplings and the energy gap between the locally excited and ionic states, which leads to a broadening of the resonance, simultaneously leads to an increase in the resonant height. This opens up wide possibilities for controlling the charge separation degree. The predictions of the theory agree with the available experimental data. The charge separation SB is predicted to accompany by SB in the excitation distribution on the branches of dyads.

Distinctive Excited State Symmetry Breaking Dynamics in Typical Donor-Acceptor-Donor Fluorophore: Strong Photoluminescence and Ultrafast Charge Separation from a Partial Charge Transfer State.

Understanding the structure-property relationships in organic semiconductors is crucial for controlling their photophysical properties and developing new optoelectronic materials. Quadrupolar molecules, donor-acceptor-donor (DAD), have attracted extensive attention in various optoelectronic applications. However, the systematic studies on the differences on photophysical properties between DAD and simple donor-acceptor (DA) chromophores are rarely reported. Herein we present a comparative study on the excited state dynamics of DA and DAD fluorescence systems using theoretical calculation and transient absorption spectroscopy. Results show that DA and DAD molecules exhibit similar excited state dynamics, which are attributed to the distinctive excited-state symmetry breaking (ESSB) phenomenon observed in a DAD system. The strong photoluminescence (PL) and ultrafast charge separation (CS) from an ESSB-induced partial charge transfer (CT) state were clearly detected in different solvent environments. These results not only offer insight into the excited state dynamics of the DAD fluorescence system but also provide some basic guidelines for designing new optoelectronic materials.

Rigid Bay-Conjugated Perylene Bisimide Rotors: Solvent-Induced Excited-State Symmetry Breaking and Resonance-Enhanced Two-Photon Absorption

Intramolecular charge transfer and excited-state symmetry breaking have a significant effect on the nonlinear optical properties of multipolar chromophores. Rigid and nonplanar perylene bisimide derivatives (PBIs) functionalized at bay positions were comparatively and comprehensively investigated. In apolar solvents, two quadrupolar molecular rotors showed an obvious decrease of the A0-0/A0-1 ratios, suggesting strong exciton coupling with the adjacent PBI units initiated by the π-π stacking. The vanishment of the preferable dimer emission in polar solvents supported the plausible phenomena of excited-state symmetry breaking, thanks to the facile rotation around the rigid linkers. Comparative femtosecond transition absorption studies confirmed their notable differences in relaxation dynamics and the generation of radical anions (PBI•-) and cations (PBI•+). The maxima two-photon absorption (2PA) wavelengths obtained for the molecular rotors were slightly red-shifted to 670 nm with intrinsic resonance-enhanced characteristics, reflecting the synergistic effect of functional positions and molecular architectures. Meanwhile, the obvious increase of significant 2PA cross-section values in polar solvents illustrated the stabilization of the symmetry-broken dipolar states. Further femtosecond Z-scan also manifested the contribution of excited-state dynamics on the nonlinear optical properties of multipolar chromophores.

Watching Excited-State Symmetry Breaking in Multibranched Push-Pull Molecules.

The emissive properties of symmetric molecules containing several donor-acceptor branches are often similar to those of the single-branched analogues. This is due to the at least partial localization of the excitation on one branch. Detailed understanding of this excited-state symmetry breaking (ES-SB) requires the ability to monitor this process in real time. Over the past few years, several spectroscopic approaches were shown to enable visualization of ES-SB and of its dynamics. They include the detection of new vibrational or electronic absorption bands associated with transitions that are forbidden in the symmetric excited state. Alternatively, ES-SB can be detected by observing transitions that become weaker or vanish upon localization of the excitation. Herein, we discuss these different approaches as well as their merits and weaknesses.

Understanding and Tailoring Excited State Properties in Solution-Processable Oligo(p-phenyleneethynylene)s: Highly Fluorescent Hybridized Local and Charge Transfer Character via Experiment and Theory.

Rod-shaped oligo(p-phenyleneethynylene) (OPE) offers an attractive π-framework for the development of solution-processable highly fluorescent molecules having tunable hybridized local and charge transfer (HLCT) excited states and (reverse) intersystem crossing ((R)ISC) channels. Herein, an HLCT oligo(p-phenyleneethynylene) library was studied for the first time in the literature in detail systematically via experiment and theory. The design, synthesis, and full characterization of a new highly fluorescent (ΦPL-solution ∼ 1) sky blue emissive 4',4‴-((2,5-bis((2-ethylhexyl)oxy)-1,4-phenylene)bis(ethyne-2,1-diyl))bis(N,N-diphenyl-[1,1'-biphenyl]-4-amine) (2EHO-TPA-PE) was also reported. The new molecule consists of a D'-Ar-π-D-π-Ar-D' molecular architecture with an extended π-spacer and no acceptor unit, and detailed structural, physicochemical, single-crystal, and optoelectronic characterizations were performed. A high solid-state quantum efficiency (ΦPL-solidstate ∼ 0.8) was achieved as a result of suppressed exciton-phonon/vibronic couplings (no π-π interactions and multiple (14 per dimeric form) strong C-H···π interactions). Strong solution-phase/solid-state dipole-dependent tunable excited state behavior (local excited (LE) → HLCT → charge transfer (CT)) and decay dynamics covering a wide spectral region were demonstrated, and the CT state was observed to be highly fluorescent despite extremely large Stokes shift (∼130 nm)/fwhm (∼125 nm) and significant charge separation (0.75 charge·nm). Employing the Lippert-Mataga model, along with detailed photophysical studies and TDDFT calculations, key relationships between molecular design-electronic structure-exciton characteristics were elucidated with regards to HLCT and hot exciton channel formations. The interstate coupling between CT and LE states and the interplay of this coupling with respect to medium polarity were explored. A key relationship between excited-state symmetry breaking process and the formation of HLCT state was discussed for TPA-ended rod-shaped OPE π-systems. (R)ISC-related delayed fluorescence (τ ∼ 2-6 ns) processes were evident following the prompt decays (∼0.4-0.9 ns) both in the solution and in the solid-state. As a unique observation, the delayed fluorescence could be tuned and facilitated via small dielectric changes in the medium. Our results and the molecular engineering perspectives presented in this study may provide unique insights into the structural and electronic factors governing tunable excited state and hot-exciton channel formations in OPEs for (un)conventional solution-processed luminescence applications.

Excited-State Symmetry Breaking in a Multiple Multipolar Chromophore Probed by Single-Molecule Fluorescence Imaging and Spectroscopy.

Excited-state symmetry breaking (ESB) has attracted much attention because it is often observed in symmetric multipolar chromophores designed as two-photon absorption/emission materials. Herein, we report an ensemble and single-molecule fluorescence imaging and spectroscopy investigation of ESB in hexakis[4-(p-dioctylaminostyryl)phenylethynyl]benzene(DB6), a two-photon absorber possessing a C6-symmetric π-D6 structure (π = hexaethynylbenzene, D = (p-dioctylaminostyryl)phenyl group) consisting of three equivalent D-π-D moieties. Ensemble and single-molecule measurements and theoretical calculations revealed that DB6 undergoes a photoabsorption process with two orthogonal transition dipole moments, whereas it fluoresces with a single transition dipole moment after one- or two-step ESB upon photoexcitation, depending on the environmental polarity. In nonpolar solvents and polymer films, one of the three D-π-D sites becomes planar, and the excited state is localized on this moiety: a [Dδ+-πδ--Dδ+]* quadrupolar state is formed. In polar solvents, the symmetry is further broken within the planarized D-π-D moiety, and the excited state is localized on one of the two D-π sites; i.e., a D-[πδ--Dδ+]* dipolar state is generated. Hence, DB6 can behave like a multichromophore with multiple emission sites in the molecule, which was demonstrated by stepwise photobleaching under photon antibunching conditions.

Excited-State Symmetry Breaking and the Laporte Rule.

Excited-state symmetry breaking (ES-SB) is common to a large number of multibranched electron donor-acceptor (DA) molecules in polar environments. During this process, the electronic excitation, originally evenly distributed over the molecule, localizes, at least partially, on one branch. Due to the absence of an unambiguous spectroscopic signature in the UV-vis region, electronic transient absorption (TA) has not been the method of choice for real-time observation of this phenomenon. Herein, we demonstrate that the Laporte rule, which states that one-photon transitions conserving parity are forbidden in centrosymmetric molecules, provides such clear signature of ES-SB in electronic TA spectroscopy. Using a dicyanoanthracene-based D-A-D dye, we show that transitions from the S1 state of this molecule, which are initially Laporte forbidden, become allowed upon ES-SB. This leads to the rise of new TA bands, whose intensity provides a direct measure of the extent of asymmetry in the excited state.

Excited-state symmetry breaking in 9,10-dicyanoanthracene-based quadrupolar molecules: the effect of donor-acceptor branch length.

Excited-state symmetry breaking is investigated in a series of symmetric 9,10-dicyanoanthracenes linked to electron-donating groups on the 2 and 6 positions via different spacers, allowing for a tuning of the length of the donor–acceptor branches. The excited-state properties of these compounds are compared with their dipolar single-branch analogues. The changes in electronic structure upon their optical excitation are monitored by transient electronic spectroscopy in the visible and near-infrared regions as well as by transient vibrational spectroscopy in the mid-infrared. Our results reveal that, with the shortest branches, electronic excitation remains distributed almost symmetrically over the molecule even in polar environments. Upon increasing the donor–acceptor distance, excitation becomes unevenly distributed and, with the longest one, it fully localises on one branch in polar solvents. The influence of the branch length on the propensity of quadrupolar dyes to undergo excited-state symmetry breaking is rationalised in terms of the balance between interbranch coupling and solvation energy.

The role of twisting in driving excited-state symmetry breaking and enhanced two-photon absorption in quadrupolar cationic pyridinium derivatives.

Two symmetric quadrupolar cationic push-pull compounds with a central electron-acceptor (N+-methylpyrydinium, A+) and different lateral electron-donors, (N,N-dimethylamino and N,N-diphenylamino, D) in a D-π-A+-π-D arrangement, were investigated together with their dipolar counterparts (D-π-A+) for their excited-state dynamics and NLO properties. As for the quadrupolar compounds, attention was focused on excited-state symmetry breaking (ESSB), which leads to a relaxed dipolar excited state. Both electron charge displacements and structural rearrangements were recognized in the excited-state dynamics of these molecules by resorting to femtosecond-resolved broadband fluorescence up-conversion experiments and advanced data analysis, used as a valuable alternative approach for fluorescent molecules compared to time-resolved IR spectroscopy, only suitable for compounds bearing IR markers. Specifically, intramolecular charge transfer (ICT) was found to be guided by ultrafast inertial solvation, while diffusive solvation can drive the twisting of lateral groups to originate twisted-ICT (TICT) states on a picosecond time scale. Yet still, only the bis-N,N-diphenylamino-substituted compound undergoes ESSB, in both highly and sparingly polar solvents, provided that it can experience large amplitude motions to a fully symmetry-broken TICT state. Besides well-known solvation effects, this structural requirement proved to be a necessary condition for these quadrupolar cations to undergo ESSB. In fact, a more efficient uncoupling between the out-of-plane D and A+ groups in the TICT state allows a greater stabilization gained through solvation, relative to the bis-N,N-dimethylamino-substituted derivative, which instead maintains its symmetry. This different behavior parallels the two-photon absorption (TPA) ability, which is greatly enhanced in the case of the bis-N,N-diphenylamino-substituted compound, paving the way for cutting-edge bio-imaging applications.

Excited-State Symmetry-Breaking Charge Separation Dynamics in Multibranched Perylene Diimide Molecules.

As one of the most promising nonfullerene acceptors for organic photovoltaics, perylene diimide (PDI)-based multibranched molecules with twisted or three-dimensional (3D) geometric structures have been developed, which effectively increase the power conversion efficiency (PCE) of organic solar cells. Understanding the structure-property relationships in multichromophoric molecular architectures at molecular and ultrafast time levels is a crucial step in establishing new design principles in organic electronic materials. For this, photodriven excited-state symmetry-breaking charge separation (SB-CS) of PDI-based multichromophoric acceptors has been proposed to improve the PCE by reducing the self-aggregation of the planar PDI monomer. Herein, we investigated the intramolecular excited-state SB-CS and charge recombination (CR) dynamics of two symmetric phenyl-methane-based PDI derivatives, a twist dimer PM-PDI2 (phenyl-methane-based PDI dimer) and a 3D configuration tetramer PM-PDI4 (phenyl-methane-based PDI tetramer), in different solvents using ultrafast femtosecond transient absorption (fs-TA) spectroscopy and quantum chemical calculations. The quantum chemical calculations and steady-state spectra show that the two PDI derivatives undergo conformational changes upon excitation, leading to their emission states that have the characteristics of partial charge-transfer (CT) exciton in all solvents. Based on the evolution of the fs-TA data, it is observed that the evolution from the CT state to SB-CS state is disfavored in a weak polar solvent, whereas clear SB-CS spectroscopic signatures of cationic and anionic PDI are observed in polar solvents. Faster CS and slower CR processes of PM-PDI4 are observed in comparison to those of PM-PDI2. The crowded space in the 3D structure shortens the distance between the branches, leading to a stronger electronic coupling at the lowest excited state and a larger negative Gibbs free energy change of PM-PDI4 relative to that of PM-PDI2, which benefits the charge separation among PDI units in PM-PDI4. Besides, the 3D structure of PM-PDI4 also restricts rotation to a surface crossing region between the excited state and ground state, thus inhibiting nonradiative CR process and increasing the CS state lifetime. Our results suggest that the kinetics of CS and CR processes are strongly related to the molecular geometric structure, and the excited-state symmetry breaking in the 3D structure acceptor has superior photogenerated charge and photovoltaic properties from the perspective of ultrafast dynamics.

Solvent tuning of photochemistry upon excited-state symmetry breaking

The nature of the electronic excited state of many symmetric multibranched donor–acceptor molecules varies from delocalized/multipolar to localized/dipolar depending on the environment. Solvent-driven localization breaks the symmetry and traps the exciton in one branch. Using a combination of ultrafast spectroscopies, we investigate how such excited-state symmetry breaking affects the photochemical reactivity of quadrupolar and octupolar A–(π-D)2,3 molecules with photoisomerizable A–π–D branches. Excited-state symmetry breaking is identified by monitoring several spectroscopic signatures of the multipolar delocalized exciton, including the S2 ← S1 electronic transition, whose energy reflects interbranch coupling. It occurs in all but nonpolar solvents. In polar media, it is rapidly followed by an alkyne–allene isomerization of the excited branch. In nonpolar solvents, slow and reversible isomerization corresponding to chemically-driven symmetry breaking, is observed. These findings reveal that the photoreactivity of large conjugated molecules can be tuned by controlling the localization of the excitation.

Modulation of circularly polarized luminescence through excited-state symmetry breaking and interbranched exciton coupling in helical push-pull organic systems.

π-Helical push-pull dyes were prepared and their (chir)optical properties were investigated both experimentally and computationally. Specific fluorescent behaviour of bis-substituted system was observed with unprecedented solvent effect on the intensity of circularly polarized luminescence (CPL, dissymmetry factor decreasing from 10-2 to 10-3 with an increase in solvent polarity) that was linked to a change in symmetry of chiral excited state and suppression of interbranched exciton coupling. The results highlight the potential of CPL spectroscopy to study and provide a deeper understanding of electronic photophysical processes in chiral π-conjugated molecules.

Excited-State Symmetry Breaking of a Symmetrical Donor−π–Donor Quadrupolar Molecule at a Polymer/Glass Interface

Symmetric multipolar (e.g., quadrupolar and octupolar) chromophores that undergo excited-state symmetry breaking in polar solvents have been drawing considerable attention for a long time as promising two-photon absorption and luminescent materials. However, this process has been generally restricted to liquid media. Herein, we report the excited-state symmetry breaking of a centrosymmetric D−π–D (donor−π–donor) quadrupolar molecule, DB2, occurring at a polymer/glass interface. In polar liquids, DB2 exhibits pronounced emission solvatochromism originating from symmetry-breaking intramolecular charge transfer in the S1 state. Single-molecule fluorescence spectroscopy shows that the fluorescence characteristics of DB2 at the interface are strikingly different from those of DB2 embedded in a polymer film, that is, the dramatic lengthening of fluorescence lifetimes and pronounced sharpening of fluorescence spectra are observed. With the aid of theoretical calculations, it is revealed that these characteristic...

Ground-State Structural Disorder and Excited-State Symmetry Breaking in a Quadrupolar Molecule.

The influence of torsional disorder around the ethynyl π-bridges of a linear D-π-A-π-D molecule on the nature of its S1 excited state was investigated using ultrafast time-resolved infrared spectroscopy. By tuning the pump wavelength throughout the S1 ← S0 absorption band, subpopulations with different extents of asymmetry could be excited. In nonpolar solvents, the equilibrated S1 state is symmetric and quadrupolar independently of the initial degree of distortion. Photoexcitation of distorted molecules is followed by planarization and symmetrization of the S1 state. Excited-state symmetry breaking is only observed in polar environments, where the equilibrated S1 state has a strong dipolar character. However, neither the extent nor the rate of symmetry breaking are enhanced in an initially distorted molecule. They are only determined by the polarity and the dynamic properties of the solvent.

Excited-State Symmetry Breaking in a Quadrupolar Molecule Visualized in Time and Space.

The influence of the length of the push-pull branches of quadrupolar molecules on their excited-state symmetry breaking was investigated using ultrafast time-resolved IR spectroscopy. For this, the excited-state dynamics of an A-π-D-π-A molecule was compared with those of an ADA analogue, where the same electron donor (D) and acceptor (A) subunits are directly linked without a phenylethynyl π-spacer. The spatial distribution of the excitation was visualized in real time by monitoring C≡C and C≡N vibrational modes localized in the spacer and acceptor units, respectively. In nonpolar solvents, the excited state is quadrupolar and the excitation is localized on the π-D-π center. In medium polarity solvents, the excitation spreads over the entire molecule but is no longer symmetric. Finally, in the most polar solvents, the excitation localizes on a single D-π-A branch, contrary to the ADA analogue where symmetry breaking is only partial.

Specific Monitoring of Excited-State Symmetry Breaking by Femtosecond Broadband Fluorescence Upconversion Spectroscopy.

Most quadrupolar molecules designed for large two-photon absorption cross section have been shown to undergo symmetry breaking upon excitation to the S1 state. This was originally deduced from their strong fluorescence solvatochromism and later visualized in real time using transient infrared spectroscopy. For molecules not containing clear IR marker modes, however, a specific real-time observation of the symmetry breaking process remains lacking. Here we show that this process can be resolved using broadband fluorescence upconversion spectroscopy by monitoring the instantaneous emission transition dipole moment. This approach is illustrated with measurements performed on two quadrupolar molecules, with only one of them undergoing excited-state symmetry breaking in polar solvents.