Elucidating Singlet-Fission-Born Multiexciton Dynamics via Molecular Engineering: A Dilution Principle Extended to Quintet Triplet Pair.

Multiexciton in singlet exciton fission represents a critical quantum state with significant implications for both solar cell applications and quantum information science. Two distinct fields of interest explore contrasting phenomena associated with the geminate triplet pair: one focusing on the persistence of long-lived correlation and the other emphasizing efficient decorrelation. Despite the pivotal nature of multiexciton processes, a comprehensive understanding of their dependence on the structural and spin properties of materials is currently lacking in experimental realizations. To address this gap in knowledge, molecular engineering was employed to modify the TIPS-tetracene structures, enabling an investigation of the structure-property relationships in spin-related multiexciton processes. In lieu of the time-resolved electron paramagnetic resonance technique, two time-resolved magneto-optical spectroscopies were implemented for quantitative analysis of spin-dependent multiexciton dynamics. The utilization of absorption and fluorescence signals as complementary optical readouts, in the presence of a magnetic field, provided crucial insights into geminate triplet pair dynamics. These insights encompassed the duration of multiexciton correlation and the involvement of the spin state in multiexciton decorrelation. Furthermore, simulations based on our kinetic models suggested a role for quintet dilution in multiexciton dynamics, surpassing the singlet dilution principle established by the Merrifield model. The integration of intricate model structures and time-resolved magneto-optical spectroscopies served to explicitly elucidate the interplay between structural and spin properties in multiexciton processes. This comprehensive approach not only contributes to the fundamental understanding of these processes but also aligns with and reinforces previous experimental studies of solid states and theoretical assessments.

Soft Bioelectronics Based on Nanomaterials.

Recent advances in nanostructured materials and unconventional device designs have transformed the bioelectronics from a rigid and bulky form into a soft and ultrathin form and brought enormous advantages to the bioelectronics. For example, mechanical deformability of the soft bioelectronics and thus its conformal contact onto soft curved organs such as brain, heart, and skin have allowed researchers to measure high-quality biosignals, deliver real-time feedback treatments, and lower long-term side-effects in vivo. Here, we review various materials, fabrication methods, and device strategies for flexible and stretchable electronics, especially focusing on soft biointegrated electronics using nanomaterials and their composites. First, we summarize top-down material processing and bottom-up synthesis methods of various nanomaterials. Next, we discuss state-of-the-art technologies for intrinsically stretchable nanocomposites composed of nanostructured materials incorporated in elastomers or hydrogels. We also briefly discuss unconventional device design strategies for soft bioelectronics. Then individual device components for soft bioelectronics, such as biosensing, data storage, display, therapeutic stimulation, and power supply devices, are introduced. Afterward, representative application examples of the soft bioelectronics are described. A brief summary with a discussion on remaining challenges concludes the review.

Application of diffusive gradient in thin films probes to monitor trace levels of labile methylmercury in freshwaters.

This study aimed to optimize the methods for sampling and analyzing methylmercury (MeHg) concentrated within diffusive gradients in thin films (DGT) and its application to different water bodies. We explored the elution solution for MeHg, comprised of 1.13 mM thiourea and 0.1M HCl, optimizing its volume to 50 mL. In addition, we found that it is necessary to analyze the entire extraction solution after adjusting its pH, to ensure completion of the ethylation reaction. The DGT samplers were deployed in two distinct aquatic environments (i.e., Okjeong Lake and Nakdong River) for up to 6 weeks, and this study demonstrated to predict the time-weighted average concentration with a diffusion coefficient of 7.65 × 10-6 cm2 s-1 for MeHg in the diffusive gel. To assess the diffusive boundary layer (DBL) effects, the DGT samplers with different agarose diffusive gel thickness were deployed. The mass of MeHg accumulated in the DGT resin at a given time decreased with increasing diffusive gel thickness, because of creating longer diffusion pathways within thicker gels. The labile MeHg concentration estimated by the DGT in Okjeong Lake and Nakdong River are found in the range of 61-111 and 55-105 pg L-1, respectively, which were found to be similar to the grab sampling data. Additionally, this study evaluated depth-dependent MeHg in Okjeong Lake. The vertical profile results showed that the concentration of MeHg at the depth of 2.3 and 15.7 m are about 1.5 and 4.6 times of the DGT installed at 0.3 m of the surface layer, respectively, suggesting potential mercury methylation in deep waters. These findings have practical implications for predicting bioavailability, assessing risks, and formulating strategies for water body management and contamination remediation.

Leveraging Charge-Transfer Interactions in Through-Space-Coupled Pentacene Dendritic Oligomer for Singlet Exciton Fission.

Singlet exciton fission in organic chromophores has received much attention during the past decade. Inspired by numerous spectroscopic studies in the solid state, there have been vigorous efforts to study singlet exciton fission dynamics in covalently bonded oligomers, which aims to investigate underlying mechanisms of this intriguing process in simplified model systems. In terms of through-space orbital interactions, however, most of covalently bonded pentacene oligomers studied so far fall into weakly interacting systems since they manifest chain-like structures based on various (non)conjugated linkers. Therefore, it remains as a compelling question to answer how through-space interactions in the solid state intervene this photophysical process since it is hypersensitive to displacements and orientations between neighboring chromophores. Herein, as one of experimental studies to answer this question, we introduced a tight-packing dendritic structure whose mesityl-pentacene constituents are coupled via moderate through-space orbital interactions. Based on the comparison with a suitably controlled dendritic structure, which is in a weak coupling regime, important mechanistic viewpoints are tackled such as configurational mixings between singlet, charge-transfer, and triplet pair states and the role of chromophore multiplication. We underscore that our through-space-coupled dendritic oligomer in a quasi-intermediate coupling regime provides a hint on the interplay of multiconfigurational excited-states, which might have drawn complexity in singlet exciton fission kinetics throughout numerous solid-state morphologies.

The passive sampler assisted human exposure risk characterization for tetrachloroethene soil vapor intrusion scenario.

The potential human health risks associated with soil vapor intrusion and volatile organic compounds (VOCs) exposure were characterized at an industrialized site by the quantification of gaseous VOCs in soil pores using a passive sampling technique. The gaseous tetrachloroethene (PCE) in soil pores varied between 12 and 5,400 µg m-3 showing 3 orders of magnitude variation with dependence on groundwater PCE concentrations. Though the PCE concentration in the air only varied between 0.45 and 1.5 µg m-3 showing negligible variations compared to the variation observed in soil pores. The PCE concentration in the air varied between 0.45 and 1.5 µg m-3. The calculation of fugacity suggested that the PCE in the test site originated from groundwater. Measured PCE in groundwater ranged from 14 to 2,400 times higher than PCE in soil gas. This indicates that conducting a vapor intrusion risk assessment using passive soil gas sampling is critical for accurate risk characterization and assessment. Estimated PCE inhalation cancer risks for street cleaners and indoor residents varied between 10-6 and 10-4 with a low plausible hazard, and between 10-3 and 10-2 with a high risk, respectively. The results of this study demonstrate that passive sampling offers a significantly lower cost and labor-intensive approach compared to traditional methods for assessing pollution distribution in contaminated sites and characterizing risks. This highlights the potential for wider application of passive sampling techniques in environmental studies.

Depth-dependent microbial communities potentially mediating mercury methylation and various geochemical processes in anthropogenically affected sediments.

Metal contamination and other geochemical alterations affect microbial composition and functional activities, disturbing natural biogeochemical cycles. Therefore, it is essential to understand the influences of multi-metal and geochemical interactions on microbial communities. This work investigated the distributions of total mercury (THg), methylmercury (MeHg), and trace metals in the anthropogenically affected sediment. The microbial communities and functional genes profiles were further determined to explore their association with Hg-methylation and geochemical features. The levels of THg and MeHg in sediment cores ranged between 10 and 40 mg/kg and 0.01-0.16 mg/kg, respectively, with an increasing trend toward bottom horizons. The major metals present at all depths were Al, Fe, Mn, and Zn. The enrichment and contamination indices confirmed that the trace metals were highly enriched in the anthropogenically affected sediment. Various functional genes were detected in all strata, indicating the presence of active microbial metabolic processes. The microbial community profiles revealed that the phyla Proteobacteria, Bacteroidetes, Bathyarchaeota, and Euryarchaeota, and the genera Thauera, Woeseia, Methanomethylovorans, and Methanosarcina were the dominant microbes. Correlating major taxa with geochemical variables inferred that sediment geochemistry substantially affects microbial community and biogeochemical cycles. Furthermore, archaeal methanogens and the bacterial phyla Chloroflexi and Firmicutes may play crucial roles in enhancing MeHg levels. Overall, these findings shed new light on the microbial communities potentially involved in Hg-methylation process and other biogeochemical cycles.

Ultrafast Symmetry-Breaking Charge Separation in a Perylene Bisimide Dimer Enabled by Vibronic Coupling and Breakdown of Adiabaticity.

Perylene bisimides (PBIs) have received great attention in their applicability to optoelectronics. Especially, symmetry-breaking charge separation (SB-CS) in PBIs has been investigated to mimic the efficient light capturing and charge generation in natural light-harvesting systems. However, unlike ultrafast CS dynamics in donor-acceptor heterojunction materials, ultrafast SB-CS in a stacked homodimer has still been challenging due to excimer formation in the absence of rigidifying surroundings such as a special pair in the natural systems. Herein, we present the detailed mechanism of ultrafast photoinduced SB-CS occurring in a 1,7-bis(N-pyrrolidinyl) PBI dimer within a cyclophane. Through narrow-band and broad-band transient absorption spectroscopy, we demonstrate that ultrafast SB-CS in the dimer is enabled by the combination of (1) vibrationally coherent charge-transfer resonance-enhanced excimer formation and (2) breakdown of adiabaticity (formation of SB-CS diabats) in the excimer state via structural and solvent fluctuation. Quantum chemical calculations also underpin that the participation of strong electron-donating substituents in overall vibrational modes plays a crucial role in triggering the ultrafast SB-CS. Therefore, our work provides an alternative route to facilitate ultrafast SB-CS in PBIs and thereby establishes a novel strategy for the design of optoelectronic materials.

Kaistella soli sp. nov., isolated from oil-contaminated experimental soil.

A light yellow-coloured, non-motile, aerobic, Gram-stain-negative, and rod-shaped bacterial strain DKR-2T was isolated from oil-contaminated experimental soil. The strain was catalase and oxidase positive, and grew at 0-1.5% (w/v) NaCl concentration, at temperature 10-35 °C, and at pH 6.0-9.5. The phylogenetic analysis suggested that the strain DKR-2T was affiliated to the genus Kaistella, with the closest species being Kaistella haifensis DSM 19056T (97.6% 16S rRNA gene sequence similarity). The principle fatty acids were iso-C15:0, summed feature 9 (iso-C17:1 ω9c and/or C16:0 10-methyl), and antiso-C15:0. The sole menaquinone was MK-6 and major polar lipid was phosphatidylethanolamin. The DNA G+C content was 39.5%. The dDDH (in silico DNA-DNA hybridization) and ANI (average nucleotide identity) values between strain DKR-2T and K. haifensis DSM 19056T were 22.4% and 79.3%, respectively. In addition, both dDDH and ANI values between strain DKR-2T and other phylogenetically related neighbours were < 25.0% and < 77.0%, respectively. In overall, the polyphasic taxonomic data presented in this study clearly indicated that strain DKR-2T represents a novel species in the genus Kaistella, for which the name Kaistella soli sp. nov. is proposed. The type strain is DKR-2T (=KACC 22070T=NBRC 114725T).

Cellulomonas fulva sp. nov., isolated from oil-contaminated soil.

A yellow-coloured, Gram-stain-positive, motile, aerobic and rod-shaped bacteria, designated DKR-3T, was isolated from oil-contaminated experimental soil. Strain DKR-3T could grow at pH 5.0-10.5 (optimum, pH 7.0-8.5), at 10-40 °C (optimum, 25-32 °C) and tolerated 3.5 % of NaCl. Phylogenetic analyses based on its 16S rRNA gene sequence indicated that strain DKR-3T formed a lineage within the family Cellulomonadaceae and was clustered with members of the genus Cellulomonas. Strain DKR-3T had highest 16S rRNA gene sequence similarities to Cellulomonas gelida DSM 20111T (98.3 %), Cellulomonas persica JCM 18111T (98.2 %) and Cellulomonas uda DSM 20107T (97.8 %). The predominant respiratory quinone was tetrahydrogenated menaquinone with nine isoprene units [MK-9(H4)]. The principal cellular fatty acids were anteiso-C15 : 0, C16 : 0 and anteiso-C17 : 0. The major polar lipids were diphosphatidylglycerol and phosphatidylglycerol. The cell-wall diamino acid was l-ornithine whereas rhamnose and glucose were the cell-wall sugars. The DNA G+C content was 74.2mol %. The genome of strain DKR-3T was 3.74 Mb and contained three putative biosynthetic gene clusters. The average nucleotide identity and digital DNA-DNA hybridization relatedness values between strain DKR-3T and its phylogenetically related members were below the species threshold values. Based on a polyphasic study, strain DKR-3T represents a novel species belonging to the genus Cellulomonas, for which the name Cellulomonas fulva sp. nov. is proposed. The type strain is DKR-3T (=KACC 22071T=NBRC 114730T).

Seasonal trends of mercury bioaccumulation and assessment of toxic effects in Asian clams and microbial community from field study of estuarine sediment.

This study investigated seasonal trends in bioaccumulation potential and toxic effects of mercury (Hg) in Asian clams (Corbicula fluminea) and microbial community. For this, a clam-exposure experiment was performed during summer, fall, and winter seasons in four different sites (HS1: control/clean site; HS2, HS3, and HS4: contaminated sites) of Hyeongsan River estuary, South Korea. Total mercury (THg) and methylmercury (MeHg) in whole sediments were highest at HS4 site during fall, sustained similar levels during winter, but decreased during summer. Unlike whole sediment, pore water reported higher levels in summer, and gradually declined during fall and winter. Asian clams from HS4 site collected during summer presented highest bioaccumulations of THg (521.52 µg/kg, dry weight) and MeHg (161.04 µg/kg, dry weight), which also correlated with the higher levels of Hg present in pore water in the same season. Moreover, biota-sediment-pore water accumulation factor (BSpAF) were comparatively greater in clams collected from HS2∼HS4 compared to HS1 sites, suggesting that porewater was a better indicator of accumulation of Hg. Upregulation of biomarker genes responsible for detoxifying process (gsts1), scavenging oxidative stress (cat), and protein reparation (hsp70 and hsp90) were observed in clams collected from HS2∼HS4. The overexpression of these biomarkers implied that Asian clams can be considered as promising warning tools for Hg-contamination. Both bacterial and metabolic diversities were negatively affected by higher levels of THg and MeHg. Phylum Proteobacteria was enriched in HS2∼HS4 compared to HS1. In contrast, phylum Bacteroidetes showed a reverse trend. The metabolic profile was highest in HS1 and lowest in HS4, revealing higher stress of Hg in HS4 site. Overall, the outcomes of this field study broaden the information on seasonal trends of bioaccumulation of Hg and its toxic effects. These findings may be helpful in Hg monitoring and management programs in other river systems.

Insights into Bacterial Community Structure and Metabolic Diversity of Mercury-Contaminated Sediments from Hyeongsan River, Pohang, South Korea.

This study investigated the bacterial community structure and metabolic diversity and their relationship with Hg and other environmental variables in sediments collected from different locations (HSR-1-HSR-6) in the Hyeongsan River estuary in South Korea. The results showed that the highest total mercury (THg) and methylmercury (MeHg) concentrations were in HSR-2, with values of 4585.3 µg/kg and 13.4 µg/kg, respectively. The lowest THg (31.9 µg/kg) and MeHg (0.1 µg/kg) concentrations were found in HSR-1. Sulfate and organic matter (OM) were more influential environmental variables, revealing a positive association with THg and MeHg and negatively affecting bacterial and metabolic diversities. Bacterial and metabolic diversities were also negatively impacted by the THg and MeHg concentrations. Proteobacteria and Bacteroidetes were abundantly distributed in all the sediments. The dominance of Proteobacteria was upscaled in all the heavily Hg-contaminated sites (HSR-2-HSR-6), and it was the only phylum that showed a significant positive correlation with THg, MeHg, and OM. The genera Sulfurovum and Sulfurimonas were abundantly observed in sites with high Hg contamination, whereas Congregibacter, Gaetbulibacter, Ilumatobacter, Methylotenera, Nevskia, and Sediminibacter were only detected in low Hg-contaminated sites (HSR-1). The community-level physiological profile data showed the highest (1.0) average well color development (AWCD) value in HSR-1 and the lowest (0.45) AWCD value in HSR-2. Overall, these results demonstrated the inhibitory effects of THg, MeHg, and other environmental variables on microbial communities and metabolic diversity. These findings broaden the current knowledge on the dynamics of bacterial and metabolic diversities in Hg-contaminated sediments and might be useful in the management of Hg pollution.

Real-time Observation of Structural Dynamics Triggering Excimer Formation in a Perylene Bisimide Folda-dimer by Ultrafast Time-Domain Raman Spectroscopy.

In π-conjugated organic photovoltaic materials, an excimer state has been generally regarded as a trap state which hinders efficient excitation energy transport. But despite wide investigations of the excimer for overcoming the undesirable energy loss, the understanding of the relationship between the structure of the excimer in stacked organic compounds and its properties remains elusive. Here, we present the landscape of structural dynamics from the excimer formation to its relaxation in a co-facially stacked archetypical perylene bisimide folda-dimer using ultrafast time-domain Raman spectroscopy. We directly captured vibrational snapshots illustrating the ultrafast structural evolution triggering the excimer formation along the interchromophore coordinate on the complex excited-state potential surfaces and following evolution into a relaxed excimer state. Not only does this work showcase the ultrafast structural dynamics necessary for the excimer formation and control of excimer characteristics but also provides important criteria for designing the π-conjugated organic molecules.

Charge-Delocalized State and Coherent Vibrational Dynamics in Rigid PBI H-Aggregates.

Herein, the ultrafast photoinduced dynamics and vibrational coherences for two perylenebisimide (PBI) H-aggregates showcase the formation of the excimer state and the delocalized radical anion state in the excited state, respectively. Using femtosecond transient absorption (fs-TA) and time-resolved impulsive stimulated Raman scattering (TR-ISRS) measurements, we unveiled excited-state dynamics of PBI H-aggregates in two aspects: (1) the intermolecular interactions between PBI units in H-aggregates induce the formation of new excited states, excimer and delocalized radical anion states, and (2) the intermolecular out-of-plane along the aggregate axis and the PBI core C═C stretch Raman modes can be a crucial indicator to understand the coherent exciton dynamics in H-aggregates. Notably, those excited-state Raman modes showed stationary peak positions during the excited-state dynamics. TR-ISRS analysis provides insights into the excited-state vibrational coherences concerning the formation of the excimer and charge-delocalized state in each aggregate system.

Noviherbaspirillum pedocola sp. nov., isolated from oil-contaminated experimental soil.

An orange-coloured, rod-shaped, and aerobic bacterial strain DKR-6 T was isolated from oil-contaminated experimental soil. The strain was Gram-stain-negative, catalase and oxidase positive, and grew at temperature 10-42 °C, at pH 5.5-9.5, and at 0-3.0% (w/v) NaCl concentration. The phylogenetic analysis and 16S rRNA gene sequence analysis suggested that the strain DKR-6 T was affiliated to the genus Noviherbaspirillum, with the closest species being Noviherbaspirillum massiliense JC206T (96.3% sequence similarity). The chemotaxonomic profiles revealed the presence of phosphatidylethanolamine, phosphatidylglycerol, diphosphatidylglycerol, and phosphatidylcholine as the principal polar lipids; C16:0, C17:0 cyclo, summed feature 3 (C16:1ω7c and/or C16: 1ω6c), and summed feature 8 (C18:1ω7c/or C18:1ω6c) as the main fatty acids; and Q-8 as a sole ubiquinone. The DNA G + C content was 61.6%. The polyphasic taxonomic features illustrated in this study clearly implied that strain DKR-6 T represents a novel species in the genus Noviherbaspirillum, for which the name Noviherbaspirillum pedocola sp. nov. is proposed with the type strain DKR-6 T (= KACC 22074 T = NBRC 114727 T).

Theoretical Engineering of Singlet Fission Kinetics in Perylene Bisimide Dimer with Chromophore Rotation.

We investigated the potential of chromophore's rotations to tune singlet fission (SF) kinetics in perylene bisimide (PBI) dimers in addition to relative horizontal displacements. The total number of 250 PBI dimers (five displacements along the long and short axis of PBI, respectively, and ten rotation angle changes from parallel to perpendicular alignment) was examined. Ground-state energies showed that dimer formation is favored in all orientations with some differences in interaction strength. Time-dependent density functional theory predicted S1 and T1 excitons' energy, and the thermodynamic feasibility of SF process was judged by the energy difference between a S1 exciton and twice of T1 excitons. In addition, we also estimated the relative rate of multiexciton generation step by the three-state kinetic model with the results of restricted active space employing double spin-flip. Nine promising orientations including two parallel PBI dimers and seven twisted ones were discussed. Wave function composition analysis showed that SF occurs mainly through the superexchange mechanism in various twisted PBI dimers, but the direct two-electron and coherent pathway could be operative at the particular positions. Quantum chemical simulations suggested the rotation as an effective tool to tune SF efficiency in PBI dimers, which is helpful to substantiate more efficient SF material.

Efficient Multiexciton State Generation in Charge-Transfer-Coupled Perylene Bisimide Dimers via Structural Control.

The singlet fission (SF) process is generally defined as the conversion of one singlet exciton (S1) into two triplet excitons (2·T1), which has the potential to overcome thermalization losses in the field of photovoltaic devices. Among the applicable compounds for SF-based photovoltaic devices, perylene bisimide (PBI) is one of the best candidates because of its electronic tunability and photostability. However, the strategy for efficient SF in PBIs remains ambiguous because of numerous competing relaxation pathways in PBI-based molecular materials. In this regard, for the first time, we observed the SF mechanism in PBI dimers by controlling the intrinsic factor (exciton coupling) and the external environment (solvent polarity and viscosity). Time-resolved spectroscopic measurements and quantum chemical simulations reveal that efficient SF occurs through the charge-transfer-assisted mechanism, entailing a large structural fluctuation. Our findings not only highlight the SF mechanism in PBI dimers but also suggest the factors responsible for an efficient SF process, which are important considerations in the design of molecular materials for photovoltaic devices.

Bis-Metal Complexes of Doubly N-Confused Dioxohexaphyrins as Potential Near-Infrared-II Photoacoustic Dyes.

We investigated the detailed photophysical properties of a series of bis-metal (Zn and Cu) dioxohexaphyrin complexes as potential second near-infrared (NIR-II)-light responsive dyes. A cisoid-configured 28π-electron-conjugated dioxohexaphyrin analogue (c-3a) containing two peculiar "confused pyrrole" moieties in the framework is identified as a reduced isomer derivative of a transoid 26π-dioxohexaphyrin (t-2a). The symmetry-altered structure of c-3a affords a heteroleptic inner environment within the NNNN/NNOO donor core, which imparts its highly flexible electronic features and nonplanar geometry. The macrocycle c-3a can be transformed into the corresponding 26π-electron congener (c-2a) having a coplanar rectangular structure by unique solvent-mediated redox reactivity. Furthermore, upon metal complexation, saddle-distorted bis-metal complexes (c-M2-2a) were formed as the 26π-conjugated structural isomer of the trans-dioxohexaphyrin species (i.e., t-M2-2a). These isoelectronic dioxohexaphyrins demonstrate precise geometry-dependent photophysical properties. Broad tailing NIR-II absorption, weak emissive character, and rapid-decay of the S1 state are observed for c-Zn2-2a. In contrast, the coplanar t-M2-2a exhibits efficient photoacoustic response upon laser excitation with NIR-II light (λ > 1000 nm). To the best of our knowledge, this is the first example of an expanded porphyrin-based photoacoustic contrast agent responsive to NIR-II light.

Tracking Structural Evolution during Symmetry-Breaking Charge Separation in Quadrupolar Perylene Bisimide with Time-Resolved Impulsive Stimulated Raman Spectroscopy.

Elucidating structural roles in photoinduced charge transfer is indispensable, as nuclear rearrangements are simultaneously usually involved in the dynamics. However, it is hard to evaluate whether the structural changes occur or not by using conventional time-resolved electronic spectroscopy. Here, time-resolved impulsive stimulated Raman spectroscopy is applied to record the evolution of vibrational snapshots during charge-separation dynamics of donor-acceptor-donor-type quadrupolar perylene bisimide in real time. Drastic frequency shifts were observed for several Raman bands with their population kinetics, thus symmetry-breaking charge separation accompanies significant structural changes, as supported by (TD)-DFT calculations. A comparison between time-resolved Raman spectra of the neutral S1 state and the radical anion species shows that the spectral signatures, especially in high-frequency regions, provide important clues to bond length alternation patterns in the PBI core.

Multiexcitonic Triplet Pair Generation in Oligoacene Dendrimers as Amorphous Solid-State Miniatures.

Singlet fission in organic semiconducting materials has attracted great attention for the potential application in photovoltaic devices. Research interests have been concentrated on identifying working mechanisms of coherent SF processes in crystalline solids as ultrafast SF is hailed for efficient multiexciton generation. However, as long lifetime of multiexcitonic triplet pair in amorphous solids facilitates the decorrelation process for triplet exciton extractions, a precise examination of incoherent SF processes is demanded in delicate model systems to represent heterogeneous structures. Heterogeneous coupling and energetics for SF were developed in our oligoacene dendrimers, which mimic complicated SF dynamics in amorphous solids. SF dynamics in dendritic structures was thoroughly investigated by time-resolved spectroscopic techniques and quantum chemical calculations in respect of the relative orientation/distance between chromophores and though-bond/-space interactions.

Near-Infrared-III-Absorbing and -Emitting Dyes: Energy-Gap Engineering of Expanded Porphyrinoids via Metallation.

The synthesis of organometallic complexes of modified 26π-conjugated hexaphyrins with absorption and emission capabilities in the third near-infrared region (NIR-III) is described. Symmetry alteration of the frontier molecular orbitals (MOs) of bis-PdII and bis-PtII complexes of hexaphyrin via N-confusion modification led to substantial metal dπ -pπ interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO-LUMO energy gap. A remarkable long-wavelength shift of the lowest S0 →S1 absorption beyond 1700 nm was achieved with the bis-PtII complex, t-Pt2 -3. The emergence of photoacoustic (PA) signals maximized at 1700 nm makes t-Pt2 -3 potentially useful as a NIR-III PA contrast agent. The rigid bis-PdII complexes, t-Pd2 -3 and c-Pd2 -3, are rare examples of NIR emitters beyond 1500 nm. The current study provides new insight into the design of stable, expanded porphyrinic dyes possessing NIR-III-emissive and photoacoustic-response capabilities.