Direct identification of interfacial degradation in blue OLEDs using nanoscale chemical depth profiling.

Understanding the degradation mechanism of organic light-emitting diodes (OLED) is essential to improve device performance and stability. OLED failure, if not process-related, arises mostly from chemical instability. However, the challenges of sampling from nanoscale organic layers and interfaces with enough analytical information has hampered identification of degradation products and mechanisms. Here, we present a high-resolution diagnostic method of OLED degradation using an Orbitrap mass spectrometer equipped with a gas cluster ion beam to gently desorb nanometre levels of materials, providing unambiguous molecular information with 7-nm depth resolution. We chemically depth profile and analyse blue phosphorescent and thermally-activated delayed fluorescent (TADF) OLED devices at different degradation levels. For OLED devices with short operational lifetimes, dominant chemical degradation mainly relate to oxygen loss of molecules that occur at the interface between emission and electron transport layers (EML/ETL) where exciton distribution is maximised, confirmed by emission zone measurements. We also show approximately one order of magnitude increase in lifetime of devices with slightly modified host materials, which present minimal EML/ETL interfacial degradation and show the method can provide insight for future material and device architecture development.

Effect of trifluoroacetic acid on InP/ZnSe/ZnS quantum dots: mimicking the surface trap and their effects on the photophysical properties.

Understanding the precise effects of defects on the photophysical properties of quantum dots (QDs) is essential to their development with near-unity luminescence. Because of the complicated nature of defects in QDs, the origins and detailed roles of the defects still remain rarely understood. In this regard, we used detailed chemical analysis to investigate the effect of surface defects on the optical properties of InP/ZnSe/ZnS QDs by introducing shell defects through controlled trifluoroacetic acid (TFA) etching. TFA treatment on the InP/ZnSe/ZnS QDs partially removed the ZnS shell as well as ligands and reduced the quantum yield by generating energetically deep surface traps. The surface defects of QDs by TFA cause charged trap sites inducing an Auger recombination process with a rate of ca. 200 ps. Based on these results, we proposed possible trap-assisted non-radiative decay pathways between the band-edge state and surface deep traps in InP/ZnSe/ZnS QDs.

Pt cocatalyst morphology on semiconductor nanorod photocatalysts enhances charge trapping and water reduction.

In photocatalysis, metal-semiconductor hybrid structures have been proposed for ideal photocatalytic systems. In this study, we investigate the effect of morphology and surface nature of Pt cocatalysts on photocatalytic hydrogen evolution activity in Pt-tipped CdSe nanorods. Three distinct morphologies of Pt cocatalysts were synthesized and employed as visible light photocatalysts. The rough tips exhibit the highest activity, followed by the round and cubic tips. Kinetic investigations using transient absorption spectroscopy reveal that the cubic tips exhibit lower charge-separated states feasible for reacting with water and water reduction rates due to their defectless surface facets. In contrast, the rough tips show a similar charge-separation value but a two-fold higher surface reaction rate than the round tips, resulting in a significant enhancement of hydrogen evolution. These findings highlight the importance of rational design on metal cocatalysts in addition to the main semiconductor bodies for maximizing photocatalytic activities.

Probing twisted intramolecular charge transfer of pyrene derivatives as organic emitters in OLEDs.

Intramolecular charge transfer (ICT) plays a critical role in determining the photophysical properties of organic molecules, including their luminescence efficiencies. Twisted intramolecular charge transfer (TICT) is a process in which structural change accompanies ICT. Herein, we used time-resolved spectroscopy to study TICT in pyrene derivatives that are promising blue organic light emitting diode (OLED) emitter candidates; these derivatives show strong solvent-dependent charge-transfer (CT) behavior with unique fluorescence properties, increased fluorescence intensity in polar solvent. Slight structural changes that do not affect excited state dynamics were observed in nonpolar solvents, while polar solvents were found to affect excited state dynamics and CT characteristics, which affect their unusual fluorescence behavior. The TICT behavior of these pyrene derivatives can be modulated through structural modification. Our study provides valuable guidelines for the control of optical properties, including the luminescence efficiencies of OLED emitters that show TICT characteristics.

Increasing the Energy Gap between Band-Edge and Trap States Slows Down Picosecond Carrier Trapping in Highly Luminescent InP/ZnSe/ZnS Quantum Dots.

Non-toxic InP-based nanocrystals have been developed for promising candidates for commercial optoelectronic applications and they still require further improvement on photophysical properties, compared to Cd-based quantum dots (QDs), for better device efficiency and long-term stability. It is, therefore, essential to understand the precise mechanism of carrier trapping even in the state-of-the-art InP-based QD with near-unity luminescence. Here, it is shown that using time-resolved spectroscopic measurements of systematically size-controlled InP/ZnSe/ZnS core/shell/shell QDs with the quantum yield close to one, carrier trapping decreases with increasing the energy difference between band-edge and trap states, indicating that the process follows the energy gap law, well known in molecular photochemistry for nonradiative internal conversion between two electronic states. Similar to the molecular view of the energy gap law, it is found that the energy gap between the band-edge and trap states is closely associated with ZnSe phonons that assist carrier trapping into defects in highly luminescent InP/ZnSe/ZnS QDs. These findings represent a striking departure from the generally accepted view of carrier trapping mechanism in QDs in the Marcus normal region, providing a step forward understanding how excitons in nanocrystals interact with traps, and offering valuable guidance for making highly efficient and stable InP-based QDs.

Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal.

Aromaticity, the special energetic stability derived from cyclic [4 n + 2]π-conjugated electronic structures, has been the topic of intense interest in chemistry because it plays a critical role in rationalizing molecular stability, reactivity, and physical/chemical properties. Recently, the pioneering work by Colin Baird on aromaticity reversal, postulating that aromatic (antiaromatic) character in the ground state reverses to antiaromatic (aromatic) character in the lowest excited triplet state, has attracted much scientific attention. The completely reversed aromaticity in the excited state provides direct insight into understanding the photophysical/chemical properties of photoactive materials. In turn, the application of aromatic molecules to photoactive materials has led to numerous studies revealing this aromaticity reversal. However, most studies of excited-state aromaticity have been based on the theoretical point of view. The experimental evaluation of aromaticity in the excited state is still challenging and strenuous because the assessment of (anti)aromaticity with conventional magnetic, energetic, and geometric indices is difficult in the excited state, which practically restricts the extension and application of the concept of excited-state aromaticity. Time-resolved optical spectroscopies can provide a new and alternative avenue to evaluate excited-state aromaticity experimentally while observing changes in the molecular features in the excited states. Time-resolved optical spectroscopies take advantage of ultrafast laser pulses to achieve high time resolution, making them suitable for monitoring ultrafast changes in the excited states of molecular systems. This can provide valuable information for understanding the aromaticity reversal. This Account presents recent breakthroughs in the experimental assessment of excited-state aromaticity and the verification of aromaticity reversal with time-resolved optical spectroscopic measurements. To scrutinize this intriguing and challenging scientific issue, expanded porphyrins have been utilized as the ideal testing platform for investigating aromaticity because they show distinct aromatic and antiaromatic characters with aromaticity-specific spectroscopic features. Expanded porphyrins exhibit perfect aromatic and antiaromatic congener pairs having the same molecular framework but different numbers of π electrons, which facilitates the study of the pure effect of aromaticity by comparative analyses. On the basis of the characteristics of expanded porphyrins, time-resolved electronic and vibrational absorption spectroscopies capture the changes in electronic structure and molecular conformations driven by the change in aromaticity and provide clear evidence for aromaticity reversal in the excited states. The approaches described in this Account pave the way for the development of new and alternative experimental indices for the evaluation of excited-state aromaticity, which will enable overarching and fundamental comprehension of the role of (anti)aromaticity in the stability, dynamics, and reactivity in the excited states with possible implications for practical applications.

Energetics of Baird aromaticity supported by inversion of photoexcited chiral [4n]annulene derivatives.

For the concept of aromaticity, energetic quantification is crucial. However, this has been elusive for excited-state (Baird) aromaticity. Here we report our serendipitous discovery of two nonplanar thiophene-fused chiral [4n]annulenes Th4 COT Saddle and Th6 CDH Screw , which by computational analysis turned out to be a pair of molecules suitable for energetic quantification of Baird aromaticity. Their enantiomers were separable chromatographically but racemized thermally, enabling investigation of the ring inversion kinetics. In contrast to Th6 CDH Screw , which inverts through a nonplanar transition state, the inversion of Th4 COT Saddle , progressing through a planar transition state, was remarkably accelerated upon photoexcitation. As predicted by Baird's theory, the planar conformation of Th4 COT Saddle is stabilized in the photoexcited state, thereby enabling lower activation enthalpy than that in the ground state. The lowering of the activation enthalpy, i.e., the energetic impact of excited-state aromaticity, was quantified experimentally to be as high as 21-22 kcal mol-1.Baird's rule applies to cyclic π-conjugated molecules in their excited state, yet a quantification of the involved energetics is elusive. Here, the authors show the ring inversion kinetics of two nonplanar and chiral [4n]annulenes to support Baird's rule from an energetic point of view.

The Extension of Baird's Rule to Twisted Heteroannulenes: Aromaticity Reversal of Singly and Doubly Twisted Molecular Systems in the Lowest Triplet State.

We have investigated the aromaticity of singly twisted Möbius aromatic and doubly twisted Hückel antiaromatic bis(palladium(II)) [36]octaphyrins in the lowest triplet state (T1 ) by spectroscopic measurements and quantum calculations. The T1 state of the singly twisted Möbius [36]octaphyrin shows broad and weak absorption spectral features that are analogous to those of antiaromatic expanded porphyrins while the T1 state of the doubly twisted Hückel [36]octaphyrin exhibits intense and distinct spectral features, indicating the aromatic nature. These results along with theoretical calculations support the hypothesis that the aromaticity is reversed in the T1 state. Furthermore, we show that the degree of structural smoothness affects the aromaticity reversal in the T1 state.

Guest-Induced Modulation of the Energy Transfer Process in Porphyrin-Based Artificial Light Harvesting Dendrimers.

A series of dendritic multiporphyrin arrays (PZnTz-nPFB; n = 2, 4, 8) comprising a triazole-bearing focal zinc porphyrin (PZn) with a different number of freebase porphyrin (PFB) wings has been synthesized, and their photoinduced energy transfer process has been evaluated. UV/vis absorption, emission, and time-resolved fluorescence measurements indicated that efficient excitation energy transfer takes place from the focal PZn to PFB wings in PZnTz-nPFB's. The triazole-bearing PZn effectively formed host-guest complexes with anionic species by means of axial coordination with the aid of multiple C-H hydrogen bonds. By addition of various anionic guests to PZnTz and PZnTz-nPFB's, strong bathochromic shifts of PZn absorption were observed, indicating the HOMO-LUMO gap (ΔEHOMO-LUMO) of PZn decreased by anion binding. Time-resolved fluorescence measurements revealed that the fluorescence emission predominantly takes place from PZn in PZnTz-nPFB's after the addition of CN-. This change was reversible because a treatment with a silver strip to remove CN- fully recovered the original energy transfer process from the focal PZn to PFB wings.

Control and Switching of Aromaticity in Various All-Aza-Expanded Porphyrins: Spectroscopic and Theoretical Analyses.

Modification of aromaticity is regarded as one of the most interesting and important research topics in the field of physical organic chemistry. Particularly, porphyrins and their analogues (porphyrinoids) are attractive molecules for exploring various types of aromaticity because most porphyrinoids exhibit circular conjugation pathways in their macrocyclic rings with various molecular structures. Aromaticity in porphyrinoids is significantly affected by structural modification, redox chemistry, NH tautomerization, and electronic states (singlet and triplet excited states). Conversely, aromaticity significantly affects the spectroscopic properties and chemical reactivities of porphyrinoids. In this context, considerable efforts have been devoted to understanding and controlling the aromaticity and antiaromaticity of porphyrinoids. Thus, a series of porphyrinoids are in the limelight, being expected to shed light on this field because they have some advantages to demonstrate the switching of aromaticity; it is possible to control the aromaticity by lowering the temperature, adding and removing the protons of expanded porphyrins, changing the chemical environment, and switching the electronic states (triplet and singlet excited states) by photoexcitation. In this regard, this Review describes the control of aromaticity in various expanded porphyrins from the spectroscopic point of view with assistance from theoretical calculations.

Boron Difluoride Complexes of Expanded N-Confused Calix[n]phyrins That Demonstrate Unique Luminescent and Lasing Properties.

Complexation of novel multiply N-confused expanded calix[n]phyrins with boron difluoride afforded a new class of cyclic BODIPY (boron-dipyrromethene) arrays. The structures of circularly arranged BODIPY subunits linked in an N-confused fashion give rise to such photophysical properties unique to the macrocycles as redshifted emission wavelengths along with apparent large Stokes shifts, long emission lifetimes, and solid-state lasing. The DFT calculations support the size-dependent excited-state dynamics of the macrocycles.

A Description of Vibrational Modes in Hexaphyrins: Understanding the Aromaticity Reversal in the Lowest Triplet State.

Aromaticity reversal in the lowest triplet state, or Baird's rule, has been postulated for the past few decades. Despite numerous theoretical works on aromaticity reversal, experimental study is still at a rudimentary stage. Herein, we investigate the aromaticity reversal in the lowest excited triplet state using a comparable set of [26]- and [28]hexaphyrins by femtosecond time-resolved infrared (IR) spectroscopy. Compared to the relatively simple IR spectra of [26]bis(rhodium) hexaphyrin (R26H), those of [28]bis(rhodium) hexaphyrin (R28H) show complex IR spectra the region for the stretching modes of conjugated rings. Whereas time-resolved IR spectra of R26H in the excited triplet state are dominated by excited state IR absorption peaks, while those of R28H largely show ground state IR bleaching peaks, reflecting the aromaticity reversal in the lowest triplet state. These contrasting IR spectral features serve as new experimental aromaticity indices for Baird's rule.

Aromaticity Reversal in the Lowest Excited Triplet State of Archetypical Möbius Heteroannulenic Systems.

The aromaticity reversal in the lowest triplet state (T1 ) of a comparable set of Hückel/Möbius aromatic metalated expanded porphyrins was explored by optical spectroscopy and quantum calculations. In the absorption spectra, the T1 states of the Möbius aromatic species showed broad, weak, and ill-defined spectral features with small extinction coefficients, which is in line with typical antiaromatic expanded porphyrins. In combination with quantum calculations, these results indicate that the Möbius aromatic nature of the S0 state is reversed to Möbius antiaromaticity in the T1 state. This is the first experimental observation of aromaticity reversal in the T1 state of Möbius aromatic molecules.

Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular circuit.

The switching phenomena of conformation with π-electronic network through deprotonation-protonation processes were investigated by employing a series of 5,20-bis(α-oligothienyl) substituted hexaphyrins(1.1.1.1.1.1). They showed significant changes in the absorption and emission spectra with deprotonation, and returned to the initial state with protonation. Through NMR measurements and single crystal X-ray diffraction analysis, we found that the 5,20-bis(α-oligothienyl) substituted hexaphyrins, which possess acyclic, helical electronic networks involving oligothienyl chains in dumbbell conformations (type-I) in a neutral form, underwent effective deprotonation upon treatment with tetrabutylammonium fluoride (TBAF) to generate the corresponding dianions, which display cyclic electronic networks with enhanced aromaticity in rectangular conformations (type-II). Our quantum calculation results provide an unambiguous description for the switchable conformation and π-conjugation, which revealed that a deprotonation-induced enhanced aromatic conjugation pathway is involved in the switchable π-electronic network.

Synthesis of [n]Cyclo-5,15-porphyrinylene-4,4'-biphenylenes Displaying Size-Dependent Excitation-Energy Hopping.

A set of 5,15-biphenylene-bridged porphyrin wheels, namely, [n]cyclo-5,15-porphyrinylene-4,4'-biphenylenes [n]CPB, have been synthesized through the platination of 5,15-bis(4-(pinacolboranyl)phenyl) nickel(II) porphyrin and subsequent reductive elimination of Pt(II) (cod)-bridged cyclic porphyrin intermediates. The calculated strain energies for [3]CPB, [4]CPB, [5]CPB, and [6]CPB are 49.3, 32.9, 23.5, and 16.0 kcal mol(-1) , respectively. UV/Vis absorption spectra and cyclic voltammetry indicated characteristic ring-size-dependent absorption-peak shifts and redox-potential shifts, which presumably reflect the degree of strain in the π-systems. Excitation-energy hopping (EEH) times were determined to be 5.1, 8.0, 8.0, and 9.6 ps for [3]CPB, [4]CPB, [5]CPB, and [6]CPB, respectively, in a pump-power-dependent TA experiment.

Switching between Aromatic and Antiaromatic 1,3-Phenylene-Strapped [26]- and [28]Hexaphyrins upon Passage to the Singlet Excited State.

We have demonstrated aromaticity reversal in the singlet excited states of internally 1,3-phenylene-strapped [26]- and [28]hexaphyrins (P26H and P28H). P26H displays a broad and reduced singlet-excited-state absorption spectrum, whereas P28H exhibits a sharp and intense singlet-excited-state absorption spectrum; both are in contrast to the ground-state absorption spectra, strongly indicating aromaticity reversal in the singlet excited state. Furthermore, magnetic and topological indices of aromaticity such as nucleus-independent chemical shift and harmonic oscillator model of aromaticity values for P26H and P28H also suggest that their singlet excited states become antiaromatic and aromatic, respectively.

Azobenzene-Bridged Porphyrin Nanorings: Syntheses, Structures, and Photophysical Properties.

Azobenzene-bridged ß-to-ß and meso-to-meso porphyrin nanorings were successfully synthesized by a palladium-catalyzed Suzuki-Miyaura coupling reaction in a logical synthesis. The dimeric structure was confirmed by XRD analysis. The azo linkages in di- and tetramers are in the all-trans conformation, whereas in the trimers one azo linkage can be interconverted between cis and trans under external stimulation. When trimeric isomers are heated to 333 K or higher, the azo linkages will be in the all-trans configurations: the pure all-trans trimer can be kept in the dark for several months. Fluorescence anisotropy and pump-power-dependent decay results revealed excitation energy transfer for azobenzene-bridged zinc-porphyrin nanorings. The distances between porphyrin units of these azobenzene-bridged porphyrin arrays are almost the same, but the exciton energy hopping (EEH) times for each wheel are markedly different. The dimer and meso-to-meso tetramer possess relatively short excitation energy transfer (EET) times (1.28 and 2.48 ps, respectively) due to their good planarity and rigidity. In contrast, the EET time for the trimeric zinc(II)-porphyrin array (6.9 ps) is relatively long due to its nonradiative decay pathway (i.e., cis/trans isomerization of azobenzene). Both di- and tetramers exhibit relatively high fluorescence quantum yields, whereas the trimers show weak emission because of structural differences.

Modulation of Axial-Ligand Binding and Releasing Processes onto the Triazole-Bearing Nickel(II) Picket-Fence Porphyrins: Steric Repulsion versus Hydrogen-Bonding Effects.

N-(p-Methoxycarbonylbenzyl) triazole (BTz) substituents have been introduced to Ni(II) porphyrins (NiPs), in which their modulated axial-coordination processes have been investigated. For this study, the two types of ligands, neutral pyridine versus anionic cyanide, were employed to investigate an effect of BTz substituents. The unique microenvironments given by the BTz substituents provided two different effects on the axial-coordination processes of NiPs on the ground and excited states: (1) steric shielding and (2) donation of hydrogen-bonding sites. The steric shielding diminished the binding affinity of pyridine, while the cooperation of hydrogen bonds extraordinarily strengthened the binding affinity of CN(-). Interestingly, it was observed that the binding of CN(-) with the supporting of BTz substituents accompanied nonplanar distortion of NiPs. Such conformational change perturbed the electronic structure of NiPs, which gave rise to the modulation of coordination processes of NiPs in the excited state. As a consequence, photoinudced ligand binding and releasing processes of four- and six-coordinated NiPs were changed into the dominant photoinduced ligand releasing process.

Reversal of Hückel (anti)aromaticity in the lowest triplet states of hexaphyrins and spectroscopic evidence for Baird's rule.

The reversal of (anti)aromaticity in a molecule's triplet excited state compared with its closed-shell singlet ground state is known as Baird's rule and has attracted the interest of synthetic, physical organic chemists and theorists because of the potential to modulate the fundamental properties of highly conjugated molecules. Here we show that two closely related bis-rhodium hexaphyrins (R26H and R28H) containing [26] and [28] π-electron peripheries, respectively, exhibit properties consistent with Baird's rule. In the ground state, R26H exhibits a sharp Soret-like band and distinct Q-like bands characteristic of an aromatic porphyrinoid, whereas R28H exhibits a broad absorption spectrum without Q-like bands, which is typical of an antiaromatic porphyrinoid. In contrast, the T-T absorption of R26H is broad, weak and featureless, whereas that of R28H displays an intense and sharp Soret-like band. These spectral signatures, in combination with quantum chemical calculations, are in line with qualitative expectations based on Baird's rule.

Phenylene ethynylene-tethered perylene bisimide folda-dimer and folda-trimer: investigations on folding features in ground and excited states.

In this work, we have elucidated in detail the folding properties of two perylene bisimide (PBI) foldamers composed of two and three PBI units, respectively, attached to a phenylene ethynylene backbone. The folding behaviors of these new PBI folda-dimer and trimer have been studied by solvent-dependent UV/Vis absorption and 1D and 2D NMR spectroscopy, revealing facile folding of both systems in tetrahydrofuran (THF). In CHCl3 the dimer exists in extended (unfolded) conformation, whereas partially folded conformations are observed in the trimer. Temperature-dependent (1) H NMR spectroscopic studies in [D8 ]THF revealed intramolecular dynamic processes for both PBI foldamers due to, on the one hand, hindered rotation around CN imide bonds and, on the other hand, backbone flapping; the latter process being energetically more demanding as it was observed only at elevated temperature. The structural features of folded conformations of the dimer and trimer have been elucidated by different 2D-NMR spectroscopy (e.g., ROESY and DOSY) in [D8 ]THF. The energetics of folding processes for the PBI dimer and trimer have been assessed by calculations applying various methods, particularly the semiempirical PM6-DH2 and the more sophisticated B97D approach, in which relevant dispersion corrections are included. These calculations corroborate the results of NMR spectroscopic studies. Folding features in the excited states of these PBI foldamers have been characterized by using time-resolved fluorescence and transient absorption spectroscopy in THF and CHCl3 , exhibiting similar solvent-dependent behavior as observed for the ground state. Interestingly, photoinduced electron transfer (PET) process from electron-donating backbone to electron-deficient PBI core for extended, but not for folded, conformations was observed, which can be explained by a fast relaxation of excited PBI stacks in the folded conformation into fluorescent excimer states.