Tailoring MIL-100(Fe)-derived catalyst for controlled carbon dioxide conversion and product selectivity.

Here in, we are reporting the effect of the catalyst particle size on the catalytic activity and product selectivity by understanding the strength of the interaction between the active catalyst and the reactants (CO2 and H2). In this regard, two catalytic systems having different active catalyst particle sizes and support surface areas were synthesized using metal-organic frameworks (MOF) (MIL-100(Fe)) having two crystal size ranges as sacrificial templates. The active catalyst having smaller nanoparticles exhibited greater chemisorption of hydrogen (Fe-H bond), resulting in heightened selectivity for paraffin due to hydrogenation of re-adsorbed olefins. Conversely, larger nanoparticles showed enhanced chemisorption of CO2 (Fe-C bond), leading to increased selectivity for olefins (O/P = 0.15). Additionally, a reduction in particle size boosts activity from 24% to 38.7% at 340 °C/20 bar. While, higher particle size enhances the selectivity towards C5+ from 11.1 to 45.6% at (300 °C/10 bar) and 9.6 to 21.3% at (340 °C/20 bar).

Cellulose acetate nanofiber modified with polydopamine polymerized MOFs for efficient removal of noxious organic dyes.

The need to effectively remove toxic organic dyes from aquatic systems has become an increasingly critical issue in the recent years. In pursuit of this objective, polydopamine (PDA)-binary ZIF-8/UiO-66 (MOFs) was synthesized and incorporated into cellulose acetate (CA), producing ZIF-8/UiO-66/PDA@CA composite nanofibers under meticulously optimized conditions. The potential of fabricated nanofibers to remove cationic methylene blue (MB) dye was investigated. Various analysis tools including FTIR, XRD, SEM, zeta potential, BET, tensile strength testing, and XPS were employed. Results revealed a substantial leap in tensile strength, with ZIF-8/UiO-66/PDA@CA registering an impressive 2.8 MPa, as a marked improvement over the neat CA nanofibers (1.1 MPa). ZIF-8/UiO-66/PDA@CA nanofibers exhibit an outstanding adsorption capacity of 82 mg/g, notably outperforming the 22.4 mg/g capacity of neat CA nanofibers. In binary dye systems, these nanofibers exhibit a striking maximum adsorption capacity of 108 mg/g, establishing their eminence in addressing the complexities of wastewater treatment. Furthermore, the adsorption data fitted to the Langmuir isotherm, and the pseudo-second-order kinetic model. The fabricated nanofiber demonstrates good reproducibility and durability, consistently upholding its performance over five cycles. This suite of remarkable attributes collectively underscores its potential as a robust, durable, and highly promising solution for the effective and efficient removal of pernicious MB dye, in the context of both water quality improvement and environmental preservation.

Optical Properties of Cationic Perylenediimide Nanowires in Aqueous Medium: Experimental and Computational Studies.

Cationic perylenediimide derivative, namely N,N'-di(2-(trimethylammoniumiodide)ethylene) perylenediimide (TAIPDI), has been synthesized and characterized in an aqueous medium by using dynamic light scattering (DLS), X-ray diffraction (XRD), fourier-transform infrared (FTIR), scanning electron microscope (SEM), and high-resolution transmission electron microscopy (HRTEM) techniques. The optical absorption and fluorescence spectra of TAIPDI revealed the formation of aggregated TAIPDI nanowires in water, but not in organic solvents. In order to control the aggregation behavior, the optical properties of TAIPDI have been examined in different aqueous media, namely cetyltrimethylammonium bromide (CTAB), and sodium dodecyl sulfate (SDS). Furthermore, the utilization of the examined TAIPDI for constructing supramolecular donor-acceptor dyad has been achieved by combining the electron accepting TAIPDI with the electron donating 4,4'-bis (2-sulfostyryl)-biphenyl disodium salt (BSSBP). The formed supramolecular dyad TAIPDI-BSSBP through the ionic and electrostatic π-π interactions have been well examined by various spectroscopic techniques, e.g., steady-state absorption and fluorescence, cyclic voltammetry, and time-correlated single-photon counting (TCSPC), and first principle computational chemistry methods. Experimental results suggested the occurring of intra-supramolecular electron transfer from BSSBP to TAIPDI with rate constant and efficiency of 4.76 × 109 s-1 and 0.95, respectively. The ease of construction, absorption in the UV-Visible region, and fast electron transfer process render the supramolecular TAIPDI-BSSBP complex as a donor-acceptor material for optoelectronic devices.

Surface-decorated porphyrinic zirconium-based metal-organic frameworks (MOFs) using post-synthetic self-assembly for photodegradation of methyl orange dye.

We report herein the surface decoration of a water-soluble free-base porphyrin, namely, 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin-tetra(p-toluenesulfonate) (H2TMPyP), over three different zirconium-based metal-organic frameworks of different linker structure and functionality; namely UiO66, UiO66-NH2, and MIP-202, via self-assembly. The synthesized MOFs along with the resulting complexes have been characterized via spectroscopic and analytical techniques (XRD, FT-IR, TEM, N2 adsorption/desorption, and laser scanning confocal microscopy). The self-assembly of H2TMPyP with the examined three MOFs was observed by using the steady-state absorption and fluorescence, as well as the fluorescence lifetime studies. It was evident that the highest complex interaction was recorded between porphyrin and UiO-66-NH2 compared with the lowest interactions between porphyrin and MIP-202. This is in good agreement with the high surface area and pore volume of UiO-66 (1100 m2 g-1 and 0.68 cm3 g-1) and compared to that of MIP-202 (94 m2 g-1 and 0.26 cm3 g-1). The photocatalytic activities of the three porphyrin entities immobilized zirconium-based MOFs were compared toward methyl orange dye degradation from aqueous solution under visible light irradiation (λex = 430 nm). The photocatalytic studies render the fabrication of the self-assembled H2TMPyP@UiO-66-NH2 composite as a promising material for dye degradation from polluted wastewater.

Effect of bismuth doping on the crystal structure and photocatalytic activity of titanium oxide.

The doping of TiO2 with metals and non-metals is considered one of the most significant approaches to improve its photocatalytic efficiency. In this study, the photodegradation of methyl orange (MO) was examined in relation to the impact of Bi-doping of TiO2. The doped TiO2 with various concentrations of metal was successfully synthesized by a one-step hydrothermal method and characterized using X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and UV-vis spectroscopy. The XRD results revealed that the anatase phase, with an average crystallite size of 16.2 nm, was the main phase of TiO2. According to the anatase texture results, it was found that the doping of TiO2 increased the specific surface area for Bi2O3@TiO2 without a change in the crystal structure or the crystal phase of TiO2. Also, XPS analysis confirmed the formation of Ti4+ and Ti3+ as a result of doping with Bi. The activities of both pure TiO2 and Bi-doped TiO2 were tested to study their ability to decolorize MO dye in an aqueous solution. The photocatalytic degradation of MO over Bi2O3@TiO2 reached 98.21%, which was much higher than the 42% achieved by pure TiO2. Doping TiO2 with Bi increased its visible-light absorption as Bi-doping generated a new intermediate energy level below the CB edge of the TiO2 orbitals, causing a shift in the band gap from the UV to the visible region, thus enhancing its photocatalytic efficiency. In addition, the effects of the initial pH, initial pollutant concentration, and contact time were examined and discussed.

Use of Singlet Oxygen in the Generation of a Mononuclear Nonheme Iron(IV)-Oxo Complex.

Nonheme iron(III)-superoxo intermediates are generated in the activation of dioxygen (O2) by nonheme iron(II) complexes and then converted to iron(IV)-oxo species by reacting with hydrogen donor substrates with relatively weak C-H bonds. If singlet oxygen (1O2) with ca. 1 eV higher energy than the ground state triplet oxygen (3O2) is employed, iron(IV)-oxo complexes can be synthesized using hydrogen donor substrates with much stronger C-H bonds. However, 1O2 has never been used in generating iron(IV)-oxo complexes. Herein, we report that a nonheme iron(IV)-oxo species, [FeIV(O)(TMC)]2+ (TMC = tetramethylcyclam), is generated using 1O2, which is produced with boron subphthalocyanine chloride (SubPc) as a photosensitizer, and hydrogen donor substrates with relatively strong C-H bonds, such as toluene (BDE = 89.5 kcal mol-1), via electron transfer from [FeII(TMC)]2+ to 1O2, which is energetically more favorable by 0.98 eV, as compared with electron transfer from [FeII(TMC)]2+ to 3O2. Electron transfer from [FeII(TMC)]2+ to 1O2 produces an iron(III)-superoxo complex, [FeIII(O2)(TMC)]2+, followed by abstracting a hydrogen atom from toluene by [FeIII(O2)(TMC)]2+ to form an iron(III)-hydroperoxo complex, [FeIII(OOH)(TMC)]2+, that is further converted to the [FeIV(O)(TMC)]2+ species. Thus, the present study reports the first example of generating a mononuclear nonheme iron(IV)-oxo complex with the use of singlet oxygen, instead of triplet oxygen, and a hydrogen atom donor with relatively strong C-H bonds. Detailed mechanistic aspects, such as the detection of 1O2 emission, the quenching by [FeII(TMC)]2+, and the quantum yields, have also been discussed to provide valuable mechanistic insights into understanding nonheme iron-oxo chemistry.

Redox-Active Azulene-based 2D Conjugated Covalent Organic Framework for Organic Memristors.

As a conjugated and unsymmetric building block composed of an electron-poor seven-membered sp2 carbon ring and an electron-rich five-membered carbon ring, azulene and its derivatives have been recognized as one of the most promising building blocks for novel electronic devices due to its intrinsic redox activity. By using 1,3,5-tris(4-aminophenyl)-benzene and azulene-1,3-dicarbaldehyde as the starting materials, an azulene(Azu)-based 2D conjugated covalent organic framework, COF-Azu, is prepared through liquid-liquid interface polymerization strategy for the first time. The as-fabricated Al/COF-Azu/indium tin oxide (ITO) memristor shows typical non-volatile resistive switching performance due to the electric filed induced intramolecular charge transfer effect. Associated with the unique memristive performance, a simple convolutional neural network is built for image recognition. After 8 epochs of training, image recognition accuracy of 80 % for a neutral network trained on a larger data set is achieved.

Water-Soluble Polythiophene-Conjugated Polyelectrolyte-Based Memristors for Transient Electronics.

The key to protect sensitive information stored in electronic memory devices from disclosure is to develop transient electronic devices that are capable of being destroyed quickly in an emergency. By using a highly water-soluble polythiophene-conjugated polyelectrolyte PTT-NMI+Br- as an active material, which was synthesized by the reaction of poly[thiophene-alt-4,4-bis(6-bromohexyl)-4H-cyclopenta(1,2-b:5,4-b')dithiophene] with N-methylimidazole, a flexible electronic device, Al/PTT-NMI+Br-/ITO-coated PET (ITO: indium tin oxide; PET: polyethylene terephthalate), is successfully fabricated. This device shows a typical nonvolatile rewritable resistive random access memory (RRAM) effect at a sweep voltage range of ±3 V and a history-dependent memristive switching performance at a small sweep voltage range of ±1 V. Both the learning/memorizing functions and the synaptic potentiation/depression of biological systems have been emulated. The switching mechanism for the PTT-NMI+Br--based electronic device may be highly associated with ion migration under bias. Once water is added to this device, it will be destructed rapidly within 20 s due to the dissolution of the active layer. This device is not only a typical transient device but can also be used for constructing conventional memristors with long-term stability after electronic packaging. Furthermore, the soluble active layer in the device can be easily recycled from its aqueous solution and reused for fabricating new transient memristors. This work offers a train of new thoughts for designing and constructing a neuromorphic computing system that can be quickly destroyed with water in the near future.

BSA Interaction, Molecular Docking, and Antibacterial Activity of Zinc(II) Complexes Containing the Sterically Demanding Biomimetic N3S2 Ligand: The Effect of Structure Flexibility.

Two zinc(II) complexes, DBZ and DBZH4, that have (ZnN3S2) cores and differ in the bridging mode of the ligating backbone, effectively bind to BSA. The binding affinity varies as DBZ > DBZH4 and depends on the ligand structure. At low concentrations, both complexes exhibit dynamic quenching, whereas at higher concentrations they exhibit mixed (static and dynamic) quenching. The energy transfer mechanism from the BSA singlet excited state to DBZ and DBZH4, is highly likely according to steady-state fluorescence and time-correlated singlet photon counting. Molecular docking was used to support the mode of interaction of the complexes with BSA and showed that DBZ had more energy for binding. Furthermore, antibacterial testing revealed that both complexes were active but to a lesser extent than chloramphenicol. In comparison to DBZH4, DBZ has higher antibacterial activity, which is consistent with the binding constants, molecular docking, and particle size of adducts. These findings may have an impact on biomedicine.

Donor-acceptor-type poly[chalcogenoviologen-alt-triphenylamine] for synaptic biomimicking and neuromorphic computing.

Polymer memristors are preeminent candidates for low-power edge computing paradigms. Poly[chalcogenoviologen-alt-triphenylamine] (PCVTPA) has been synthesized by direct coupling of chalcogeno-viologen as electron acceptor and 4-(bromomethyl)-N-(4-(bromo-methyl)phenyl)-N-phenylaniline as electron donor. The introduction of chalcogen atoms (S, Se, Te) into viologen scaffolds can greatly improve electrical conductive, electrochemical, and electrochromic properties of the materials when compared with the conventional viologens. Taking PTeVTPA as an example, the as-fabricated electronic device with a configuration of Al/PTeVTPA/ITO exhibits excellent multilevel storage and history-dependent memristive switching performance. Associated with the unique memristive behavior, the PTeVTPA-based device can not only be used to emulate the synaptic potentiation/depression, the human's learning and memorizing functions, and the transition from short-term synaptic plasticity to long-term plasticity but also carry out decimal arithmetic operations as well. This work will be expected to offer a train of new thought for constructing high-performance synaptic biomimicking and neuromorphic computing system in the near future.

Green Synthesis of Nano-Zero-Valent Iron Using Ricinus Communis Seeds Extract: Characterization and Application in the Treatment of Methylene Blue-Polluted Water.

In this study, the removal of methylene blue dye (MB) from aqueous solution was examined using a novel green adsorbent to overcome the obstacles encountered in chemical methods. Ricinus communis (RC) aqueous seeds extract was herein used as a reducing and capping agent to synthesize a novel nano-zero-valent iron (RC-nZVI) for the adsorption of harmful MB. Structural and morphological characterization of the synthesized RC-nZVI were performed using several techniques, e.g., steady-state absorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and zeta potential. The maximum efficiency of the removal was 96.8% at pH 6 and 25 °C. According to the kinetics study results, the adsorption process obeys the pseudo-first-order model. The experimental equilibrium data were fitted to the Freundlich isotherm model, the maximum adsorption capacity reached was 61.37 mg·g-1, and the equilibrium parameters were determined. The synthesized RC-nZVI possesses good reusability and can be considered as a potential economic and environmentally friendly adsorbent.

90% yield production of polymer nano-memristor for in-memory computing.

Polymer memristors with light weight and mechanical flexibility are preeminent candidates for low-power edge computing paradigms. However, the structural inhomogeneity of most polymers usually leads to random resistive switching characteristics, which lowers the production yield and reliability of nanoscale devices. In this contribution, we report that by adopting the two-dimensional conjugation strategy, a record high 90% production yield of polymer memristors has been achieved with miniaturization and low power potentials. By constructing coplanar macromolecules with 2D conjugated thiophene derivatives to enhance the π-π stacking and crystallinity of the thin film, homogeneous switching takes place across the entire polymer layer, with fast responses in 32 ns, D2D variation down to 3.16% ~ 8.29%, production yield approaching 90%, and scalability into 100 nm scale with tiny power consumption of ~ 10-15 J/bit. The polymer memristor array is capable of acting as both the arithmetic-logic element and multiply-accumulate accelerator for neuromorphic computing tasks.

Water soluble porphyrin as optical sensor for the toxic heavy metal ions in an aqueous medium.

Here we report the photophysical and sensing properties of the aqueous solution of meso-tetra(N-methyl-4-pyridyl)porphyrin toluene sulfonate (TMPP) for simultaneous detection of toxic metal ions in an aqueous medium by using different physiochemical methods such as UV-vis absorption, steady state and time resolved fluorescence, stopped flow, and cyclic voltammetry. The steady-state absorption and fluorescence spectra in organic solvents (EtOH, DMSO, DMF, MeOH and ACN) showed the formation of monomer form (λmaxabs = 426 nm and λmaxflu = 654 and 715 nm). In THF and water, different spectral features were recorded suggested the formation of aggregated forms in both solvents. The formation of aggregated form in water was confirmed by recording the remarkable fluorescence quenching of the singlet excited TMPP with increasing the concentrations of TMPP. In cationic micelles (CTAB), both the absorption and fluorescence spectra were significantly decreased with increasing the concentrations of CTAB with a break at CMC value at 6.0 × 10-5 M. In an anionic micelle (SDS), the CMC value was found to be 1.0 × 10-4 M. Upon interacting with different metal ions, the absorption and fluorescence spectra of TMPP showed different features depending on the metal ions. While the optical studies of TMPP showed no significant interaction in the presence of Mn+2, Co+2, Ba2+, and Ni+2, TMPP showed that it can function as a single optical chemical sensor for the toxic metal ions in water, particularly Hg+2, Pb+2, Cu+2, and Cd+2 ions.

Self-assembly of porphyrin on graphene oxide in aqueous medium: fabrication, characterization, and photocatalytic studies.

We herein report the supramolecular self-assembly of a water soluble porphyrin, namely, 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin-tetra(p-toluenesulfonate) (TMPyP), on the surface of graphene oxide (GO). The fabricated GO nanosheet and GO@TMPyP hybrid material composite have been characterized by using various spectroscopic and analytical techniques, e.g., scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared (FT-IR) spectroscopy. The steady state absorption measurements of the GO@TMPyP self-assembly showed a significant red shift (∼20 nm) compared to those of the control TMPyP in water. The steady state fluorescence measurements showed a significant fluorescence quenching of the singlet excited state of TMPyP in the presence of GO. These findings suggest the electron transfer reaction from TMPyP to GO. The time resolved fluorescence measurements showed a considerable decrease in the lifetime of the singlet state of TMPyP in the presence of GO, from which the rate and efficiency of the electron transfers from TMPyP to GO were determined to be 1.93 × 109 s-1 and 91%, respectively. The transient absorption measurements showed a considerable quenching of the triplet excited state of TMPyP in the self-assembly. All these findings confirm the occurrence of efficient electronic interactions between TMPyP and GO in both the ground and excited states. In addition, the fabricated GO@TMPyP showed high photocatalytic activity for the degradation of methylene blue (MB) and methyl orange (MO) mixed dye pollutants in water under visible light irradiation.

Epidermal Growth Factor Receptor-Targeted Multifunctional Photosensitizers for Bladder Cancer Imaging and Photodynamic Therapy.

The in vitro and in vivo anticancer activity of iodinated photosensitizers (PSs) with and without an erlotinib moiety was investigated in UMUC3 [epidermal growth factor (EGFR)-positive] and T24 (EGFR-low) cell lines and tumored mice. Both the erlotinib-conjugated PSs 3 and 5 showed EGFR target specificity, but the position-3 erlotinib-PS conjugate 3 demonstrated lower photodynamic therapy efficacy than the corresponding non-erlotinib analogue 1, whereas the conjugate 5 containing an erlotinib moiety at position-17 of the PS showed higher tumor uptake and long-term tumor cure (severe combined immunodeficient mice bearing UMUC3 tumors). PS-erlotinib conjugates in the absence of light were ineffective in vitro and in vivo, but robust apoptotic and necrotic cell death was observed in bladder cancer cells after exposing them to a laser light at 665 nm. In contrast to 18F-fluorodeoxyglucose, a positron emission tomography agent, the position-17 erlotinib conjugate (124I-analogue 6) showed enhanced UMUC3 tumor contrast even at a low imaging dose of 15 µCi/mouse.

Graphene oxide decorated with zinc oxide nanoflower, silver and titanium dioxide nanoparticles: fabrication, characterization, DNA interaction, and antibacterial activity.

The fabrication, characterization, and antibacterial activity of novel nanocomposites based on graphene oxide (GO) nanosheets decorated with silver, titanium dioxide nanoparticles, and zinc oxide nanoflowers were examined. The fabricated nanocomposites were characterized by various techniques including X-ray diffraction, ultraviolet-visible light absorption and fluorescence spectroscopy, Brunauer-Emmett-Teller theory analysis, Fourier transform infrared, and scanning electron microscopy. The antibacterial activity of the GO-metal oxide nanocomposites against two Gram-positive and two Gram-negative bacteria was examined by using the standard counting plate methodology. The results showed that the fabricated nanocomposites on the surface of GO could inhibit the growth of microbial adhered cells, and consequently prevent the process of biofilm formation in food packaging and medical devices. To confirm the antibacterial activity of the examined GO-nanocomposites, we examined their interactions with bovine serum albumin (BSA) and circulating tumor DNA (ctDNA) by steady-state fluorescence spectroscopy. Upon addition of different amounts of fabricated GO-nanocomposites, the fluorescence intensities of the singlet states of BSA and ctDNA were considerably quenched. The higher quenching was observed in the case of GO-Ag-TiO2@ZnO nanocomposite compared with other control composites.

Simple, selective detection and efficient removal of toxic lead and silver metal ions using Acid Red 94.

Toward the goal of detecting toxic elements and removing them from drinking water, we report herein the utilization of Acid Red 94 (AR94) in sensing the hazardous metal ions in water. Among the various examined metal ions (Ag+, Pb2+, K+, Mn2+, Zn2+, La3+, Hg2+, Ca2+, Cd2+, Co2+, and Ni2+), the UV-visible absorption spectra showed high selectivity and sensitivity for toxic silver and lead metal ions in an aqueous solution. The observed absorption spectral changes and the rapid color changes confirm complex formation between AR94 and both Ag+ and Pb2+ metal ions. The emission measurements showed the significant fluorescence quenching of the singlet excited state of AR94 in the presence of Ag+ and Pb2+ metal ions suggesting the formation of an irradiative dye-metal complex under the prevailing experimental conditions. In order to remove the accumulated complexes of AR94 with silver metal ions, safe and harmless mesoporous titanium dioxide was utilized efficiently in removing the complexes with adsorption capacities of 91% at 30 minutes. These findings suggest a simple, fast and efficient method for both detecting silver in water, and removing the formed AR94-metal complexes in water. In addition, AR94 is shown to be a good sensor for the presence of Ag and Pb nanoparticles, NPs, in aqueous solution. The absorption and emission spectra of AR94 showed significant changes that may be rationalized by the strong electromagnetic coupling induced by NPs plasmonic effects. These findings render AR94 a sensitive and selective sensor and a visual indicator for the qualitative and quantitative detection of silver ions, lead ions and their nanoparticles.

Energy transfer between two light harvesting phthalocyanine derivatives as model for artificial photosynthetic antenna: Laser photolysis studies.

The singlet-singlet and triplet-triplet energy transfer studies between two light harvesting phthalocyanine derivatives namely, zinc tert-butyl phthalocyanine ZnTBPc, and zinc octabutyloxy phthalocyanine ZnOBuPc, have been investigated to mimic the efficient energy-transfer process among the chlorophyll units in the natural photosynthesis. Optical absorption and emission studies showed the strong absorption and fluorescence bands for ZnOBuPc in the NIR region, which are largely red-shifted compared to that of the ZnTBPc. The strong overlap between the emission spectrum of ZnTBPc and the absorption spectrum of ZnOBuPc in toluene suggests the occurrence of the energy transfer from the singlet ZnTBPc (1.80 eV) to the singlet ZnOBuPc (1.59 eV). From the time-resolved fluorescence technique, the rate of energy transfer process was found to be 6.79 × 107 s-1. From the nanosecond laser photolysis measurements, the energy transfer from the triplet ZnTBPc to the lower lying triplet ZnOBuPc was clearly observed with a rate of 5.77 × 105 s-1. These observations suggest the usefulness of the examined combination (ZnOBuPc/ZnTBPc) as a simple model for the artificial antenna in the photosynthetic systems.

Intramolecular electron transfer of light harvesting perylene-pyrene supramolecular conjugate.

Electronic interactions between the cationic N,N'-bis(2(trimethylammonium iodide) ethylene)perylene-3,4,9,10-tetracarboxyldiimide (TAIPDI) with two electron donors, namely, pyrene (Py) and 1-pyrenesulfonic acid sodium salt (PySA), have been investigated. The spectroscopic studies showed the formation of the supramolecular conjugate between TAIPDI and PySA via ionic interaction, but not with Py. Density functional theory (DFT) combined with a natural energy decomposition analysis (NEDA) technique showed an S-like structure of the supramolecular conjugate TAIPDI-PySA via an ionic interaction. The formation constant of the TAIPDI-PySA supramolecular conjugate was determined to be 3.0 × 104 M-1, suggesting a fairly stable complex formation. The excited state events were monitored by both steady state and time-resolved emission techniques. Upon excitation, the quenching pathways via the singlet-excited states of TAIPDI and PySA involved the intramolecular electron transfer from the electron donating PySA to the electron accepting TAIPDI with a rate constant of 1.10 × 1011 s-1 and a quantum yield of 0.99. The thermodynamic parameters of the supramolecular TAIPDI-PySA conjugate have been determined using the stopped-flow technique.

Long-Lived Photoexcited State of a Mn(IV)-Oxo Complex Binding Scandium Ions That is Capable of Hydroxylating Benzene.

Photoexcitation of a MnIV-oxo complex binding scandium ions ([(Bn-TPEN)MnIV(O)]2+-(Sc(OTf)3)2) in a solvent mixture of trifluoroethanol and acetonitrile (v/v = 1:1) resulted in formation of the long-lived photoexcited state, which can hydroxylate benzene to phenol. The photohydroxylation of benzene by [(Bn-TPEN)MnIV(O)]2+-(Sc(OTf)3)2 was made possible by electron transfer from benzene to the long-lived 2 E excited state of [(Bn-TPEN)MnIV(O)]2+-(Sc(OTf)3)2 to produce a benzene radical cation, which reacted with water as revealed by laser-induced transient absorption measurements.