Elucidating Inner Workings of Naturally Sourced Organic Optoelectronic Materials with Ultrafast Spectroscopy

Recent advances in sustainable optoelectronics including photovoltaics, light-emitting diodes, transistors, and semiconductors have been enabled by π-conjugated organic molecules. A fundamental understanding of light-matter interactions involving these materials can be realized by time-resolved electronic and vibrational spectroscopies. In this Minireview, the photoinduced mechanisms including charge/energy transfer, electronic (de)localization, and excited-state proton transfer are correlated with functional properties encompassing optical absorption, fluorescence quantum yield, conductivity, and photostability. Four naturally derived molecules (xylindein, dimethylxylindein, alizarin, indigo) with ultrafast spectral insights showcase efficient energy dissipation involving H-bonding networks and proton motions, which yield high photostability. Rational design principles derived from such investigations could increase the efficiency for light harvesting, triplet formation, and photosensitivity for improved and versatile optoelectronic performance.     

Ultrafast energy transfer and structural dynamics in DNA

Ultrafast structural dynamics concomitant to excitation energy transfer in DNA has been studied using a pair of pyrene-labeled DNA bases. The temporal evolution of the femtosecond pump-probe spectra reveals the existence of two electronic coupling pathways, through-base stack and through-space, which lead to excitation energy transfer and excimer formation even when the labeled DNA bases are separated by one AT base pair. The electronic coupling which mediates through-base stack energy transfer is so strong that a new absorption band arises in the excited-state absorption spectrum within 300 fs. From the analysis of time-dependent spectral shifts due to through-space excimer formation, the local structural dynamics and flexibility of DNA are characterized on the picosecond and nanosecond time scale.     

The effect of broken conjugation on the excited state: ether linkage in the cyano-substituted poly(p-phenylene vinylene) conjugated polymer poly(2,5,2',5'-tetrahexyloxy-8,7'-dicyano-di-p-phenylene vinylene)

We investigate the effect of broken conjugation on the excited state dynamics of excimers in cyano-substituted phenylene-vinylene polymers. We compare previous studies on the well-characterized poly(2,5,2',5'-tetrahexyloxy-8,7'-dicyano-di-p-phenylene vinylene) (CN-PPV) with poly[oxa-1,4-phenylene-1,2-(1-cyano)-ethenylene-2,5-dioctyloxy-1,4-phenylene-1,2-(2-cyano)-ethenylene-1,4-phenylene] (CN-ether-PPV), in which the conjugation is disrupted by the insertion of an oxygen atom within the polymer backbone. Despite the broken conjugation, the spectroscopic behavior of the two materials is similar, indicating that the cyano group dominates the photophysics in these materials. The emission in CN-ether-PPV is due to a single-chain exciton in solution and due to an interchain excimer in thin film, as previously reported for CN-PPV; however, the excimer absorption and emission in thin film are blueshifted by approximately 0.2 eV relative to CN-PPV, implying that the excimer in CN-ether-PPV is less stable. Furthermore, substitution of an ether group along the chain results in decay times in both solution and film that are twice as long than in CN-PPV due to the broken conjugation which restricts the exciton within a conjugation segment and reduces its access to internal quenching sites. These properties result in a decay time of 14 ns for CN-ether-PPV film, one of the longest decay times observed in a conjugated polymer film. The long lifetime indicates a large exciton diffusion length, making these species particularly vulnerable to quenching by other materials. This work has implications for the design of conjugated polymers for efficient optoelectronic devices, such as photovoltaics.     

Excited-state energy transfers in single-walled carbon nanotubes functionalized with tethered pyrenes

Single-walled carbon nanotubes were co-functionalized with pyrenemethanol and 3,5-dihexadecanyloxybenzyl alcohol in different ratios with the purpose of altering the content of pyrene moieties tethered to the nanotube surface. The functionalized nanotube samples were characterized by using established instrumental techniques. The absorption and emission results of the samples suggest that there are significant “intramolecular” excited-state energy transfers from both pyrene monomer and excimer to the linked nanotube, though the energy transfer efficiencies may be different between the monomer and excimer. The excimer formation can be limited by reducing the pyrenemethanol fraction to simplify the excited state processes, but contributions from the luminescence of the well-functionalized carbon nanotubes in the same wavelength region becomes an additional complication. Mechanistic implications of the photophysical results are discussed.     

Adjusting Aggregation Modes and Photophysical and Photovoltaic Properties of Diketopyrrolopyrrole-Based Small Molecules by Introducing B←N Bonds

The packing mode of small-molecular semiconductors in thin films is an important factor that controls the performance of their optoelectronic devices. Designing and changing the packing mode by molecular engineering is challenging. Three structurally related diketopyrrolopyrrole (DPP)-based compounds were synthesized to study the effect of replacing C−C bonds by isoelectronic dipolar B←N bonds. By replacing one of the bridging C−C bonds on the peripheral fluorene units of the DPP molecules by a coordinative B←N bond and changing the B←N bond orientation, the optical absorption, fluorescence, and excited-state lifetime of the compounds can be tuned. The substitution alters the preferential aggregation of the molecules in the solid state from H-type (for C−C) to J-type (for B←N). Introducing B←N bonds thus provides a subtle way of controlling the packing mode. The photovoltaic properties of the compounds were evaluated in bulk heterojunctions with a fullerene acceptor and showed moderate performance as a consequence of suboptimal morphologies, bimolecular recombination, and triplet-state formation.     

9,9-二-(3-(9-苯咔唑基))-2,7-芘基芴的光电性质

芴类化合物作为有机电致发光材料近年来引起了人们的广泛关注, 其具有高亮度和高工作效率等性能. 本论文采用量子化学方法研究了一种新型的芴类发光材料, 9,9-二-(3-(9-苯咔唑基))-2,7-芘基芴的光电性质. 具体研究内容包括基态和激发态几何结构、前线分子轨道、能隙、电离能、电子亲和势、重组能以及吸收光谱和发射光谱等. 理论计算结果表明, 9,9-二-(3-(9-苯咔唑基))-2,7-芘基芴发射光谱为450.6 nm, 其在电致发光器件应用上是一种具有开发前景和实用价值的蓝光发光材料.     

Controlling the π‐Stacking Behavior of Pyrene Derivatives: Influence of H‐Bonding and Steric Effects in Different States of Aggregation

The performance of opto‐electronic devices built from low‐molecular‐weight dye molecules depends crucially on the stacking properties and the resulting coupling of the chromophoric systems. Herein we investigate the influence of H‐bonding amide and bulky substituents on the π‐stacking of pyrene‐containing small molecules in dilute solution, as supramolecular aggregates, and in the solid state. A set of four pyrene derivatives was synthesized in which benzene or 4‐tert‐butyl benzene was linked to the pyrene unit either through an ester or an amide. All four molecules form supramolecular H‐aggregates in THF solution at concentrations above 1×10^?4 mol L^?1. These aggregates were transferred on a solid support and crystallized. We investigate: the excimer formation rates within supramolecular aggregates; the formation of H‐bonds as well as the optical changes during the transition from the amorphous to the crystalline state; and the excimer to monomer fluorescence ratio in crystalline films at low temperatures. We reveal that in solution supramolecular aggregation depends predominantly on the pyrene chromophores. In the crystalline state, however, the pyrene stacking can be controlled gradually by H‐bonding and steric effects. These results are further confirmed by molecular modeling. This work bears fundamental information for tailoring the solid state of functional optoelectronic materials.     

Intramolecular charge transfer in 1:1 Cu(II)/pyrenylcyclam dendrimer complexes

Two newly synthesized pyrenylcyclam dendrons (1 and 2) exhibit a new emission band centered at 450 nm when coordinated with copper triflate. Observed fluorescence shifts induced by coordinative metalation indicate an unusual intramolecular charge transfer from a pyrenyl excited state to the coordinated metal ion that competes with pyrene excimer formation. This interaction likely proceeds by photoexcitation of pi-complex of the appended arene, followed by intramolecular charge transfer within the dendritic 1:1 cyclam/metal complex, effecting reduction of the bound Cu(II) metal ion. The appended dendritic groups not only decrease the equilibrium binding constant with Cu(II) but also participate in a new excited-state pathway as an alternative to energy-dissipative excimer formation.     

Probes of the microenvironments of the cationic copolymers of styrene and vinylbenzenetrialkylammonium halides

The microenvironments of the cationic copolymers of styrene and vinylbenzenetrialkylammonium halides were explored by use of fluorescence spectroscopy. 5-Dimethylamino-1-naphthalenesulfonate (DANS) and 1-pyrenebutyrate (PB) were the fluorescent probes selected to bind to the polymers. The fluorescence energy of the former responds to the polarity or hydrophobicity of the microenvironment, whereas the absorption and fluorescence of the latter reveal the extent of ground-state and excited-state interactions. Polyelectrolyte coiling occurs in proportion to the fraction of binding sites occupied with charge-neutralizing, probe molecules. The bound DANS probe shows that coiling makes the binding-site environment more hydrophobic, and the bound PB probe shows that coiling facilitates excimer formation not only with nearest-neighbor pyrene moieties, but also with non-nearest neighbors. With methyl groups at the quaternary nitrogen binding sites, pyrene moiety interactions preceding excimer fluorescence occur in both ground and excited states. When the methyl groups are replaced with butyl or pentyl groups, pyrene excimers still form in the excited state, but the weak, hydrophobic interactions of the pyrene ground state decrease, because the longer alkyl groups serve as hosts for the hydrophobic pyrene moieties.     

新型三嗪桥连的双1,8-萘酰亚胺衍生物的合成及其光物理行为

以1,8-萘酰亚胺和三聚氯氰为主要原料, 合成了两种由三嗪环桥连的双1,8-萘酰亚胺化合物3 和5. 采用紫外-可见光谱和荧光光谱等手段考察了两种化合物在不同溶剂中的光物理行为. 与参比化合物N-丁基-1,8-萘酰亚胺相比, 在二氯甲烷、三氯甲烷和甲醇等极性溶剂中, 化合物3和5除了在短波区(λ<400 nm)存在1,8-萘酰亚胺的特征荧光发射峰外, 在长波区(>450 nm)均产生一个较强的新荧光发射峰, 表现出分子内激基缔合物的光物理行为. 与化合物5相比, 由于化合物3特殊的构象异构, 其荧光强度发生严重的猝灭. 在非极性溶剂甲基环己烷中, 化合物5 由于存在较强的分子间氢键作用而聚集, 受激后形成了较稳定的分子间激基缔合物, 但未观察到明显的分子内激基缔合物的形成. 在甲苯溶剂中, 化合物3和5与甲苯分子形成了激基复合物, 并未形成分子内激基缔合物. 进一步研究3和5的固态激发态性质, 发现化合物3和5的固体薄膜受激后分别在465和469 nm处出现激基缔合物的特征荧光发射峰.     

Theoretical studies on conjugated phenyl-cored thiophene dendrimers for photovoltaic applications

Pi-conjugated dendrimers are an important class of materials for optoelectronic devices, especially for light-harvesting systems. We report here a theoretical investigation of the optical response and of the excited-state properties of three-arm and four-arm phenyl-cored dendrimers for photovoltaic applications. A variety of theoretical methods are used and evaluated against each other to calculate vertical transition energies, absorption and excitation spectra with vibronic structure, charge transport, and excitonic behavior upon photoexcitation and photoemission processes. Photophysical phenomena in these dendrimers are, in general, better explained with ab initio methods rather than with semiempirical techniques. Calculated reorganization energies were found to correlate well with the device photocurrent data where available. The excitons formed during photoexcitation are calculated to be more delocalized than the ones formed after vibrational relaxation in the excited states for fluorescence emission. The localization of excitons in emission processes is a result of geometrical changes in the excited state coupled with vibronic modes. Correlated electron-hole pair diagrams illustrate breaking of pi-conjugation in three-arm dendrimers due to meta linkage of arms with the core, whereas four-arm dendrimers are not affected by such breaking due to presence of ortho and para branching. Yet, ortho branching causes large twist angles between the core and the arms that are detrimental to pi-electron system delocalization over the structure.     

Excited states of TAPT-PDA COF spectra based on first principles and quantum chemical calculations

Improving two-dimensional (2D) materials is crucial for achieving integrated, intelligent, and multifunctional development of optoelectronic materials. Thus, it is essential to have a comprehensive understanding of the excitation mechanisms of covalent organic framework (COF) materials in order to prepare and modify 2D materials. This study focuses primarily on the optoelectronic properties of TAPT-PDA COF. First, the geometric structure of TAPT-PDA COF, which has a pore size of 32.4 Å and a width of 1.75 Å, was determined using first principles and quantum chemical methods. Second, the hole–electron distribution of each excited state of TAPT-PDA COF was analyzed for oscillator strengths exceeding 0.01. Additionally, the electron transition mechanism for each excited state following photon absorption was investigated. Finally, the study presents the UV–Vis and electronic circular dichroism spectra of TAPT-PDA COF based on quantitative calculations. To validate the results, the chirality of TAPT-PDA COF was experimentally confirmed. The graphs and data obtained from the experiments demonstrate that TAPT-PDA COF exhibits excellent optoelectronic performance and has significant potential for application in optoelectronic devices.     

Existence of intramolecular triplet excimer of bis(9-fluorenyl)methane: phosphorescence and delayed fluorescence spectroscopic and ab initio studies

A concerted computational and experimental study has been undertaken to probe the conformational structure and excited-state dynamics of bis(9-fluorenyl)methane (BFM). We have observed that the relative intensity of the delayed excimer fluorescence of BFM is greatly enhanced in comparison with that of the normal fluorescence. This is presumably because the relative concentration of the triplet excimer is enhanced in comparison with the singlet excimer. B3LYP DFT/6-31G(d) calculations indicate that the sandwich conformer of BFM in the singlet ground state is unstable, whereas that in the triplet excited state has a bound state, being very slightly higher in internal and Gibbs free energies than that of the lowest state of the near-orthogonal conformer.     

Excited-state proton-relay dynamics of 7-hydroxyquinoline controlled by solvent reorganization in room temperature ionic liquids

The excited-state triple proton relay of 7-hydroxyquinoline (7HQ) along a hydrogen-bonded methanol chain in room temperature ionic liquids (RTILs) has been investigated using picosecond time-resolved fluorescence spectroscopy. The rate constant of the proton relay in a methanol-added RTIL is found to be slower by an order of magnitude than that in bulk methanol and to have unity in its kinetic isotope effect. These suggest that the excited-state tautomerization dynamics of 7HQ in methanol-added RTILs is mainly controlled by the solvent reorganization dynamics to form a cyclically hydrogen-bonded complex of 7HQ·(CH(3)OH)(2) upon absorption of a photon due to high viscosity values of RTILs. Because the cyclic complex of 7HQ·(CH(3)OH)(2) at the ground state is unstable in RTILs, the collision-induced slow formation of the cyclic complex should take place upon excitation prior to undergoing subsequent intrinsic proton transfer rapidly.     

Photophysics and nonlinear absorption of peripheral-substituted zinc phthalocyanines

The photophysical properties, such as the UV-vis absorption spectra, triplet transient difference absorption spectra, triplet excited-state extinction coefficients, quantum yields of the triplet excited state, and lifetimes of the triplet excited state, of 10 novel zinc phthalocyanine derivatives with mono- or tetraperipheral substituents have been systematically investigated in DMSO solution. All these complexes exhibit a wide optical window in the visible spectral range and display long triplet excited-state lifetimes (140-240 mus). It has been found that the complexes with tetrasubstituents at the alpha-positions exhibit a bathochromic shift in their UV-vis absorption spectra, fluorescence spectra, and triplet transient difference absorption spectra and have larger triplet excited-state absorption coefficients. The nonlinear absorption of these complexes has been investigated using the Z-scan technique. It is revealed that all complexes exhibit a strong reverse saturable absorption at 532 nm for nanosecond and picosecond laser pulses. The excited-state absorption cross sections were determined through a theoretical fitting of the experimental data using a five-band model. The complexes with tetrasubstituents at the alpha-positions exhibit larger ratios of triplet excited-state absorption to ground-state absorption cross sections (sigma T/sigma g) than the other complexes. In addition, the wavelength-dependent nonlinear absorption of these complexes was studied in the range of 470-550 nm with picosecond laser pulses. All complexes exhibit reverse saturable absorption in a broad visible spectral range for picosecond laser pulses. Finally, the nonlinear transmission behavior of these complexes for nanosecond laser pulses was demonstrated at 532 nm. All complexes, and especially the four alpha-tetrasubstituted complexes, exhibit stronger reverse saturable absorption than unsubstituted zinc phthalocyanines due to the larger ratio of their excited-state absorption cross sections to their respective ground-state absorption cross sections.     

Synthesis,characterization, and optoelectronic properties of hyperbranched polyfluorenes containing pendant benzylether dendrons

Linear polyfluorenes with low generation of side benzylether dendrons ( PLG0 , PLG1 ) and hyperbranched polyfluorenes with 1,3,5‐benzene branch unit ( PHG0 and PHG1 ) were prepared by the Suzuki coupling reaction to investigate the structural effect on optoelectronic properties. Their optical properties, both in solution and film state, were investigated using absorption and photoluminescence (PL) spectra. The excimer emission of polyfluorene at about 530 nm, induced by thermal annealing, was completely suppressed by the hyperbranched structure, but the suppression was not obvious by the side benzylether dendrons. The optoelectronic performance of the EL devices (ITO/PEDOT:PSS/polymer/Ca/Al) was strongly dependent upon chemical structures of the emitting polyfluorenes. The hyperbranched PHG0 with zero generation of benzylether side groups revealed the best device performance, with maximal luminance and maximal luminance efficiency of 2350 cd/m² and 0.33 cd/A, respectively. The results suggest that incorporation of branch units with low generation of benzylether dendrons is an effective way to improve annealing stability and EL performance of the polyfluorenes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5945–5958, 2008     

Accessing the triplet state of perylenediimide by radical-enhanced intersystem crossing

Owing to their exceptional photophysical properties and high photostability, perylene diimide (PDI) chromophores have found various applications as building blocks of materials for organic electronics. In many light-induced processes in PDI derivatives, chromophore excited states with high spin multiplicities, such as triplet or quintet states, have been revealed as key intermediates. The exploration of their properties and formation conditions is thus expected to provide invaluable insight into their underlying photophysics and promises to reveal strategies for increasing the performance of optoelectronic devices. However, accessing these high-multiplicity excited states of PDI to increase our mechanistic understanding remains a difficult task, due to the fact that the lowest excited singlet state of PDI decays with near-unity quantum yield to its ground state. Here we make use of radical-enhanced intersystem crossing (EISC) to generate the PDI triplet state in high yield. One or two 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) stable radicals were covalently attached to the imide position of PDI chromophores with and without p-tert-butylphenoxy core substituents. By combining femtosecond UV-vis transient absorption and transient electron paramagnetic resonance spectroscopies, we demonstrate strong magnetic exchange coupling between the PDI triplet state and TEMPO, resulting in the formation of excited quartet or quintet states. Important differences in the S₁ state deactivation rate constants and triplet yields are observed for compounds bearing PDI moieties with different core substitution patterns. We show that these differences can be rationalized by considering the varying importance of competitive excited state decay processes, such as electron and excitation energy transfer. The comparison of the results obtained for different PDI–TEMPO derivatives leads us to propose design guidelines for optimizing the efficiency of triplet sensitization in molecular assemblies by EISC.

The triplet state of PDI can be sensitized efficiently by radical-enhanced intersystem crossing. A detailed study of several related structures allows us to propose new strategies to optimize triplet formation in materials for optoelectronic devices.     

聚电解质对离子型染料形成激基缔合物和能量传递的增强作用

在水溶液中聚苯乙烯磺酸钠(Napss)可以增加离子型染料吖啶橙和吡红的局部浓度,从而显著地促进吖啶橙形成激基缔合物,增大吖啶橙-吡红能量传递效率.在10^-^4mol.dm^-^3Napss存在下,形成吖啶橙激基缔合物的速率常数比Napps不存在时增大两个数量级,而离解常数小一个数量级.表明在聚电解质存在下,两个吖啶橙分子在基态时相互靠近处于液基缔合物的构型.加入小分子电解质可阻止染料形成激基缔合物.     

Determination of the excited state dipole moment of fluorenone using the method of solvatochromism

The absorption spectra and steady state fluorescence spectra of fluorenone have been obtained at room temperature for various concentrations in a series of non polar and polar solvents. The concentration effect shows two fluorescence bands, one at shorter wavelength due to monomer and another at longer wavelength due to excimer formation by triplet-triplet annihilation process. The excited state dipole moments of both monomer and dimer are calculated by the method of solvatochromism. A reasonable agreement has been observed between the values obtained by the method of solvatochromism and electrochromism.