Synthesis,Photophysics and Nonlinear Optical Properties of Stilbenoid Pyrimidine‐Based Dyes Bearing Methylenepyran Donor Groups

The nonlinear properties and the photophysical behavior of two π‐conjugated chromophores that incorporate an electron‐deficient pyrimidine core (A) and γ‐methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes’ scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end‐groups. This latter structural parameter also has a strong influence on the excited‐state dynamics, which leads to a very efficient fluorescence quenching.     

Singlet fission in a hexacene dimer: energetics dictate dynamics

Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large.

We report the synthesis and photophysical characterization of highly exoergic singlet fission in a hexacene dimer revealing exciton dynamics that follow the energy gap law.     

Excitonic energy transfer in light-harvesting complexes in purple bacteria

Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. It is found that the inclusion of long-range dipolar interactions in the two methods results in significant increase in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking caused by the dimerization of BChls and dipolar couplings, such dependence has been largely suppressed. In the studies of coupled-ring systems, both methods reveal an interesting role of dipolar interactions in increasing energy transfer efficiency by introducing multiple intra/inter-ring transfer paths. Importantly, the time scale (4 ps) of inter-ring exciton transfer obtained from polaron dynamics is in good agreement with previous studies. In a double-ring LH2 system, non-nearest neighbor interactions can induce symmetry breaking, which leads to global and local minima of the average trapping time in the presence of a non-zero dephasing rate, suggesting that environment dephasing helps preserve quantum coherent energy transfer when the perfect circular symmetry in the hypothetic system is broken. This study reveals that dipolar coupling between chromophores may play an important role in the high energy transfer efficiency in the LH systems of purple bacteria and many other natural photosynthetic systems.     

Exciton migration in rigid-rod conjugated polymers: an improved Förster model

The dynamics of interchain and intrachain excitation energy transfer taking place in a polyindenofluorene endcapped with perylene derivatives is explored by means of ultrafast spectroscopy combined with correlated quantum-chemical calculations. The experimental data indicate faster exciton migration in films with respect to solution as a result of the emergence of efficient channels involving hopping between chains in close contact. These findings are supported by theoretical simulations based on an improved Forster model. Within this model, the rates are expressed according to the Fermi golden rule on the basis of (i) electronic couplings that take account of the detailed shape of the excited-state wave functions (through the use of a multicentric monopole expansion) and (ii) spectral overlap factors computed from the simulated acceptor absorption and donor emission spectra with explicit coupling to vibrations (considered within a displaced harmonic oscillator model); inhomogeneity is taken into account by assuming a distribution of chromophores with different conjugation lengths. The calculations predict faster intermolecular energy transfer as a result of larger electronic matrix elements and suggest a two-step mechanism for intrachain energy transfer with exciton hopping along the polymer backbone as the limiting step. Injecting the calculated hopping rates into a set of master equations allows the modeling of the dynamics of exciton transport along the polyindenofluorene chains and yields ensemble-averaged energy-transfer rates in good agreement with experiment.     

Exciton Coupling of Surface Complexes on a Nanocrystal Surface

Exciton coupling may arise when chromophores are brought into close spatial proximity. Herein the intra‐nanocrystal exciton coupling of the surface complexes formed by coordination of 8‐hydroxyquinoline to ZnS nanocrystals (NCs) is reported. It is studied by absorption, photoluminescence (PL), PL excitation (PLE), and PL lifetime measurements. The exciton coupling of the surface complexes tunes the PL color and broadens the absorption and PLE windows of the NCs, and thus is a potential strategy for improving the light‐harvesting efficiency of NC solar cells and photocatalysts.     

DNA molecular photonics

Synthetic DNA conjugates in which one or both ends of a short duplex is capped by a stilbene chromophore have been prepared and characterized crystallographically. Selective excitation of the chromophore can be used to initiate electron transfer processes in which a nucleobase serves as either an electron donor or an electron acceptor. These processes include hole- and electron injection and hole migration. The dynamics of these processes and its dependence on distance, driving force, and base sequence have been investigated by means of femtosecond time-resolved spectroscopy. Duplexes with identical chromophores at both ends have been used to study both the dynamics of electron transfer processes and exciton coupling between the two chromophores by means of circular dichroism spectroscopy. Duplexes with different chromophores can also be used to study distance dependence of both electron transfer and exciton coupling.     

Solvent effects on competitive intramolecular electron transfer and energy transfer in a covalently linked porphyrin-phthalocyanine heterodimer

Photophysical properties of a porphyrin-phthalocyanine heterodimer covalently linked with a dipentoxy chain have been studied.Absorption spectra show that there is weak exciton coupling between the two chromophores in the ground state.Fluorescence spectra show that intramolecular energy transfer from porphyrin to phthalocyanine moiety occurs in competition with electron transfer.The efficiency of these two processes depends upon the mutual orientation of the two chromophores.The effect of solvent polarity on the intramolecular processes is also discussed.     

Exciton‐Vibrational Couplings in Homo‐ and Heterodimer Stacks of Perylene Bisimide Dyes within Cyclophanes: Studies on Absorption Properties and Theoretical Analysis

The optical properties of a series of three cyclophanes comprising either identical or different perylene bisimide (PBI) chromophores were studied by UV/Vis absorption spectroscopy and their distinctive spectral features were analyzed. All the investigated cyclophanes show significantly different absorption features with respect to the corresponding constituent PBI monomers indicating strong coupling interactions between the PBI units within the cyclophanes. DFT calculations suggest a π‐stacked arrangement of the PBI units at close van der Waals distance in the cyclophanes with rotational displacement. Simulations of the absorption spectra based on time‐dependent quantum mechanics properly reproduced the experimental spectra, revealing exciton‐vibrational coupling between the chromophores both in homo‐ and heterodimer stacks. The PBI cyclophane comprising two different PBI chromophores represents the first example of a PBI heterodimer stack for which the exciton coupling has been investigated. The quantum dynamics analysis reveals that exciton coupling in heteroaggregates is indeed of similar strength as for homoaggregates.     

Bis(merocyanine) Hetero-Folda-Dimers: Evaluation of Exciton Coupling between Different Types of π-Stacked Chromphores

Exciton coupling between different types of chromophores has been rarely investigated. Herein, a systematic study on the exciton coupling between merocyanine chromophores of different conjugation length with varying excited state energies is presented. In this work well-defined hetero-dimer stacks were obtained upon folding of bis(merocyanine) dyes in nonpolar solvents. They show distinctly different absorption properties in comparison with the spectra of the single chromophores, revealing a significant coupling between the different chromophores. The simulated absorption spectra obtained from time-dependent density functional theory (TD-DFT) calculations are in good agreement with the experimental spectra. Our theoretical analysis based on an extension of Kasha's exciton theory discloses strong coupling between the dyes’ transition dipole moments despite of an excited-state energy difference of 0.60 eV between the chromophores.     

Two-photon transitions in quadrupolar and branched chromophores: experiment and theory

A combined experimental and theoretical study is conducted on a series of model compounds in order to assess the combined role of branching and charge symmetry on absorption, photoluminescence, and two-photon absorption (TPA) properties. The main issue of this study is to examine how branching of quadrupolar chomophores can lead to different consequences as compared to branching of dipolar chromophores. Hence, three structurally related pi-conjugated quadrupolar chromophores symmetrically substituted with donor end groups and one branched structure built from the assembly of three quadrupolar branches via a common donor moiety are used as model compounds. Their photophysical properties are studied using UV-vis spectroscopy, and the TPA spectra are determined through two-photon excited fluorescence experiments using femtosecond pulses in the 500-1000 nm range. Experimental studies are complemented by theoretical calculations. The applied theoretical methodology is based on time-dependent density functional theory, the Frenkel exciton model, and analysis in terms of the natural transition orbitals of relevant electronic states. Theory reveals that a symmetrical intramolecular charge transfer from the terminal donating groups to the middle of the molecule takes place in all quadrupolar chromophores upon photoexcitation. In contrast, branching via a central electron-donating triphenylamine moiety breaks the quadrupolar symmetry of the branches. Consequently, all Frank-Condon excited states have significant asymmetric multidimensional charge-transfer character upon excitation. Subsequent vibrational relaxation of the branched chromophore in the excited state leads to a localization of the excitation and fluorescence stemming from a single branch. As opposed to what was earlier observed when dipolar chromophores are branched via the same common electron-donating moiety, we find only a slight enhancement of the maximum TPA response of the branched compound with respect to an additive contribution of its quadrupolar branches. In contrast, substantial modifications of the spectral shape are observed. This is attributed to the subtle interplay of interbranch electronic coupling and asymmetry caused by branching.     

Hyperfluorescent polymers enabled by through-space charge transfer polystyrene sensitizers for high-efficiency and full-color electroluminescence

Fluorescent polymers are suffering from low electroluminescence efficiency because triplet excitons formed by electrical excitation are wasted through nonradiative pathways. Here we demonstrate the design of hyperfluorescent polymers by employing through-space charge transfer (TSCT) polystyrenes as sensitizers for triplet exciton utilization and classic fluorescent chromophores as emitters for light emission. The TSCT polystyrene sensitizers not only have high reverse intersystem crossing rates for rapid conversion of triplet excitons into singlet ones, but also possess tunable emission bands to overlap the absorption spectra of fluorescent emitters with different bandgaps, allowing efficient energy transfer from the sensitizers to emitters. The resultant hyperfluorescent polymers exhibit full-color electroluminescence with peaks expanding from 466 to 640 nm, and maximum external quantum efficiencies of 10.3–19.2%, much higher than those of control fluorescent polymers (2.0–3.6%). These findings shed light on the potential of hyperfluorescent polymers in developing high-efficiency solution-processed organic light-emitting diodes and provide new insights to overcome the electroluminescence efficiency limitation for fluorescent polymers.

Hyperfluorescent polymers with high efficiency and full-color electroluminescence are developed by using through-space charge transfer polystyrenes as sensitizers for exciton utilization and fluorescent chromophores as emitters for light emission.     

CD spectra of polynuclear complexes of diimine ligands: theoretical and experimental evidence for the importance of internuclear exciton coupling

We have recently reported on dinuclear complexes Lambda,Lambda-[Co(2)L(2)Cl(2)]CoCl(4) of two novel chiral ligands (1a and 1b) which contain pyridyl-imine chelate groups (Telfer, S. G.; Sato, T.; Kuroda, R. Chem. Commun. 2003, 1064-1065). The absolute configuration of the cobalt(II) centers was unambiguously assigned by X-ray crystallography. However, the sign of the exciton couplets in their CD spectra was opposite to that expected on the basis of the stereochemistry of the metal centers. We present a rationalization of these anomalous spectra in terms of an "internuclear" exciton coupling model which takes into account the coupling of chromophores located on different metal centers. We have performed a series of semiempirical (ZINDO) calculations which provide quantitative support to this model. These findings show that the absolute configuration of the metal centers in a polynuclear complex may be incorrectly assigned on the basis of CD data if internuclear coupling effects are not taken into consideration. We summarize the CD spectral data of number of other chiral polynuclear complexes from the literature, including dinuclear complexes bridged by the 2,2'-bipyrimidine ligand, complexes of the HAT ligand, and dinuclear triple-stranded helicates. The amplitude of the CD spectra of many of these complexes is not additive with the number of chromophores. These anomalous spectra can be accounted for by taking internuclear coupling effects into consideration.     

Exciton coupling in coordination compounds

This Perspective reviews the impact of exciton coupling on the spectroscopic properties of coordination compounds. Exciton coupling features arise in electronic absorption and circular dichroism spectra when chromophores are brought into close spatial proximity, for example by coordination to a metal centre. The analysis of these features can reveal much information such as the geometry of a complex and its absolute configuration. The extension of the exciton coupling model to polynuclear metallosupramolecular arrays is discussed.     

Dephasing and Dissipation in a Source–Drain Model of Light‐Harvesting Systems

The energy transport process in natural‐light‐harvesting systems is investigated by solving the time‐dependent Schrödinger equation for a source–network–drain model incorporating the effects of dephasing and dissipation, owing to coupling with the environment. In this model, the network consists of electronically coupled chromophores, which can host energy excitations (excitons) and are connected to source channels, from which the excitons are generated, thereby simulating exciton creation from sunlight. After passing through the network, excitons are captured by the reaction centers and converted into chemical energy. In addition, excitons can reradiate in green plants as photoluminescent light or be destroyed by nonphotochemical quenching (NPQ). These annihilation processes are described in the model by outgoing channels, which allow the excitons to spread to infinity. Besides the photoluminescent reflection, the NPQ processes are the main outgoing channels accompanied by energy dissipation and dephasing. From the simulation of wave‐packet dynamics in a one‐dimensional chain, it is found that, without dephasing, the motion remains superdiffusive or ballistic, despite the strong energy dissipation. At an increased dephasing rate, the wave‐packet motion is found to switch from superdiffusive to diffusive in nature. When a steady energy flow is injected into a site of a linear chain, exciton dissipation along the chain, owing to photoluminescence and NPQ processes, is examined by using a model with coherent and incoherent outgoing channels. It is found that channel coherence leads to suppression of dissipation and multiexciton super‐radiance. With this method, the effects of NPQ and dephasing on energy transfer in the Fenna–Matthews–Olson complex are investigated. The NPQ process and the photochemical reflection are found to significantly reduce the energy‐transfer efficiency in the complex, whereas the dephasing process slightly enhances the efficiency. The calculated absorption spectrum reproduces the main features of the measured counterpart. As a comparison, the exciton dynamics are also studied in a linear chain of pigments and in a multiple‐ring system of light‐harvesting complexes II (LH2) from purple bacteria by using the Davydov D₁ ansatz. It is found that the exciton transport shows superdiffusion characteristics in both the chain and the LH2 rings.     

DNA-mediated exciton coupling and electron transfer between donor and acceptor stilbenes separated by a variable number of base pairs

The synthesis, steady-state spectroscopy, and transient absorption spectroscopy of DNA conjugates possessing both stilbene electron donor and electron acceptor chromophores are described. These conjugates are proposed to form nicked DNA dumbbell structures in which a stilbenedicarboxamide acceptor and stilbenediether donor are separated by variable numbers of A-T or G-C base pairs. The nick is located either adjacent to one of the chromophores or between two of the bases. Thermal dissociation profiles indicate that stable structures are formed possessing as few as two A-T base pairs. Circular dichroism (CD) spectra in the base pair region are characteristic of B-DNA duplex structures, whereas CD spectra at longer wavelengths display two bands attributed to exciton coupling between the two stilbenes. The sign and intensity of these bands are dependent upon both the distance between the chromophores and the dihedral angle between their transition dipoles [Deltaepsilon approximately Rda(-2) sin(2theta)]. Pulsed laser excitation of the stilbenediamide results in creation of the acceptor-donor radical ion pair, which decays via charge recombination. The dynamics of charge separation and charge recombination display an exponential distance dependence, similar to that observed previously for systems in which guanine serves as the electron donor. Unlike exciton coupling between the stilbenes, there is no apparent dependence of the charge-transfer rates upon the dihedral angle between donor and acceptor stilbenes. The introduction of a single G-C base pair between the donor and acceptor results in a change in the mechanism for charge separation from single step superexchange to hole hopping.     

CD spectra of d-f heterobimetallic helicates with segmental di-imine ligands

We have investigated the CD spectra of a series of enantiomerically pure heterobimetallic helicates, Lambda,Lambda-[LnCr(1)(3)](6+) (Ln = Eu, Gd, Tb), which contain segmental di-imine ligands. For the mononuclear precursor of these helicates, Lambda-[Cr(1)(3)](3+), a positive exciton couplet was observed around 330 nm, as expected for a tris(di-imine) complex with this absolute configuration. The titration of Ln(III) ions into a solution of this complex leads to the formation of Lambda,Lambda-[LnCr(1)(3)](6+). During this process, the CD signal was observed to invert to give a signal which was negative at lower energies. We investigated the observed changes in the CD spectra using a ZINDO-based computational method which we have previously developed. We were able to show that the exciton coupling of the chromophores coordinated to the Cr and Ln ions give rise to CD signals of opposite phase, despite having the same nominal absolute configuration. Exciton coupling between chromophores located on different metal centers ("internuclear" exciton coupling) is also predicted to have a significant impact on the observed spectrum. We were able to "deconstruct" the observed CD spectra into a set of competing exciton coupling effects and show that the sign of these spectra does not correlate with the absolute configuration of the individual metal centers.     

An activated scheme for resonance energy transfer in conjugated materials

Energy transfer mechanism in conjugated materials has been demonstrated with an activated expression, which is equivalent to Fermi's golden rule. Spectral overlap integrals obtained from simulated spectra of model chromophores agree very well with the results obtained with the activated formula. Although this approach works best for chromophores with spectral profiles resembling a Gaussian distribution, the activated expression formula also performs quite well for chromophores with vibronically resolved spectra. Activation energies for exciton hopping can also be predicted using a phonon coupled exciton relaxation scheme. The accuracy of predictions with this new approach is quite attractive and hence should allow practical applications.     

Linear absorbance of the pheophorbide-a butanediamine dendrimer P(4) in solution: computational studies using a mixed quantum classical methodology

The linear absorbance of a particular chromophore complex P(4) dissolved in ethanol is computed. P(4) is formed by a butanediamine dendrimer to which four pheophorbide-a molecules are covalently linked. The computations utilize a mixed quantum classical methodology and different approximations are compared. The electronic states of the P(4) chromophores which form Frenkel excitons in the excited states are treated quantum mechanically, whereas the intramolecular, intermolecular, as well as solvent coordinates are described classically. The computations use an improved exciton model, where the charge and transition densities of the chromophores are described by atomic partial charges, derived from a fit of the respective ab initio electrostatic potentials. Room temperature molecular dynamics simulations of all nuclear coordinates result in a time-dependent exciton model. It includes modulations of chromophore excitation energies due to charge density coupling between all chromophores as well as between the chromophores and solvent molecules, and, finally, modulations of the interchromophore excitonic couplings. The different approximations to the absorbance agree rather well. In particular, they confirm the reliability of adiabatic excitonic states which energies and oscillator strengths are altered by the overall temporal evolution of P(4) conformations. The fluctuations of solute-solvent interactions have a significantly larger effect on the absorbance broadening than the excitonic couplings but cannot completely explain the measured spectrum. The additional account for intrachromophore vibrations overcomes this discrepancy.     

Energy and electron transfer in enhanced two-photon-absorbing systems with triplet cores

Enhanced two-photon-absorbing (2PA) systems with triplet cores are currently under scrutiny for several biomedical applications, including photodynamic therapy (PDT) and two-photon microscopy of oxygen. The performance of so far developed molecules, however, is substantially below expected. In this study we take a detailed look at the processes occurring in these systems and propose ways to improve their performance. We focus on the interchromophore distance tuning as a means for optimization of two-photon sensors for oxygen. In these constructs, energy transfer from several 2PA chromophores is used to enhance the effective 2PA cross section of phosphorescent metalloporphyrins. Previous studies have indicated that intramolecular electron transfer (ET) can act as an effective quencher of phosphorescence, decreasing the overall sensor efficiency. We studied the interplay between 2PA, energy transfer, electron transfer, and phosphorescence emission using Rhodamine B-Pt tetrabenzoporphyrin (RhB-PtTBP) adducts as model compounds. 2PA cross sections (sigma2) of tetrabenzoporphyrins (TBPs) are in the range of several tens of GM units (near 800 nm), making TBPs superior 2PA chromophores compared to regular porphyrins (sigma2 values typically 1-2 GM). Relatively large 2PA cross sections of rhodamines (about 200 GM in 800-850 nm range) and their high photostabilities make them good candidates as 2PA antennae. Fluorescence of Rhodamine B (lambda(fl) = 590 nm, phi(fl) = 0.5 in EtOH) overlaps with the Q-band of phosphorescent PtTBP (lambda(abs) = 615 nm, epsilon = 98 000 M(-1) cm(-1), phi(p) approximately 0.1), suggesting that a significant amplification of the 2PA-induced phosphorescence via fluorescence resonance energy transfer (FRET) might occur. However, most of the excitation energy in RhB-PtTBP assemblies is consumed in several intramolecular ET processes. By installing rigid nonconducting decaproline spacers (Pro10) between RhB and PtTBP, the intramolecular ETs were suppressed, while the chromophores were kept within the F?rster r0 distance in order to maintain high FRET efficiency. The resulting assemblies exhibit linear amplification of their 2PA-induced phosphorescence upon increase in the number of 2PA antenna chromophores and show high oxygen sensitivity. We also have found that PtTBPs possess unexpectedly strong forbidden S0 --> T1 bands (lambda(max) = 762 nm, epsilon = 120 M-1 cm-1). The latter may overlap with the laser spectrum and lead to unwanted linear excitation.     

DNA as helical ruler: exciton-coupled circular dichroism in DNA conjugates

The structure and properties of oligonucleotide conjugates possessing stilbenedicarboxamide chromophores at both ends of a poly(dA):poly(dT) base-pair domain of variable length have been investigated using a combination of spectroscopic and computational methods. These conjugates form capped hairpin structures in which one stilbene serves as a hairpin linker and the other as a hydrophobic end-cap. The capping stilbene stabilizes the hairpin structures by ca. 2 kcal/mol, making possible the formation of a stable folded structure containing a single A:T base pair. Exciton coupling between the stilbene chromophores has little effect on the absorption bands of capped hairpins. However, exciton-coupled circular dichroism (EC-CD) can be observed for capped hairpins possessing as many as 11 base pairs. Both the sign and intensity of the EC-CD spectrum are sensitive to the number of base pairs separating the stilbene chromophores, as a consequence of the distance and angular dependence of exciton coupling. Calculated spectra obtained using a static vector model based on canonical B-DNA are in good agreement with the experimental spectra. Molecular dynamics simulations show that conformational fluctuations of the capped hairpins result in large deviations of the averaged spectra in both the positive and negative directions. These results demonstrate for the first time the ability of B-DNA to serve as a helical ruler for the study of electronic interactions between aligned chromophores. Furthermore, they provide important tests for atomistic theoretical models of DNA.