Complexation of Flavonoids: Spectral Phenomena, Regioselectivity, Interplay with Charge and Proton Transfer.

The review compiles information on the spectral classification of flavonoids, the changes in their electronic structure upon complex formation, and the manifestation of these changes in the absorption and emission spectra. Part of the review is devoted to the regioselectivity of the complex formation process, including types of complexation sites, the structure of chelates and 'open' complexes, and the correlation between the structure of complexes and their spectral properties. The interplay between complex formation and other processes occurring in flavonoids during electronic excitation is also considered, such as intramolecular inter-fragment charge transfer (ICT) and intramolecular proton transfer (ESIPT). The review also contains systematic data on the study of regioselectivity and spectral properties of flavone complexes, obtained by the author and their colleagues over the past decades.

Synthesis, Spectral Characterization and Photoluminescence of 3-chloro-6-methoxy-2-(methylsulfanyl)quinoxaline in Different Solvents: An Experimental and Theoretical Investigation Using DFT.

In the present work, we synthesized 3-chloro-6-methoxy-2-(methyl sulfanyl) quinoxaline (3MSQ) using a microwave-assisted synthesis method. The physicochemical structural analysis of the synthesized compound utilizing 1H-NMR, 13C-NMR, and FT-IR spectroscopy techniques. The photophysical properties of 3MSQ was examined through absorption and fluorescence spectroscopy. Spectroscopic analyses revealed a bathochromic shift in both absorption and fluorescence spectra, attributed to the π → π* transition. Ground and excited state dipole moments was experimentally determined using the solvatochromic shift method, employing various correlations such as Lippert's, Bakhshiev's, Kawski-Chamma-Viallet's equations, and solvent polarity parameters. Our findings indicate that the excited state dipole moments exceed those of the ground state, suggesting increased polarity in the excited state. Further, the while detailed bond length, bond angles, dihedral angles, Mulliken charge distribution, ground state dipole moments and HOMO-LUMO energy gap estimated through ab initio computations using Gaussian-09W. The value of energy band gap obtained from both the methods are in good agreement. Furthermore, employing DFT computational analysis, we identified reactive centers such as electrophilic and nucleophilic sites using molecular electrostatic potential (MESP) 3D plots. Additionally, CIE chromaticity analysis was performed to understand the photoluminescent properties of 3MSQ. The insights derived from these analyses contribute to a better understanding of the molecule's electronic structure, photophysical properties, and solute-solvent interactions, thus providing valuable information regarding its behaviour and characteristics under diverse conditions. These results contribute to a comprehensive understanding of the molecular structure and properties of 3-chloro-6-methoxy-2-(methyl sulfanyl) quinoxaline (3MSQ).

Radiative balance and temperature of differently pigmented cotton canopies.

Pigments are known to modify the spectral properties of foliage, which in turn affect the amount of radiant energy stored by the plant canopy. Studies have shown that red pigments (anthocyanin) increase leaf absorptivity of solar radiation, but little is known about their effect on canopy net radiation and temperature. We hypothesized that increased absorptivity of solar radiation caused by red pigments would result in higher canopy temperature when compared to that of a green canopy. To better understand the role of red pigments on canopy net radiation and temperature, we conducted a study where we measured leaf spectral properties, canopy spectral reflectivity, stomatal conductance, net radiation, and leaf and canopy temperature of red and green cotton (Gossypium hirsutum L.) canopies. On average, albedo of the red canopy was 0.02 lower than that of the green canopy, and most of the differences in reflected solar irradiance were in near-infrared wavelengths. Red canopy had greater net radiation than the green canopy throughout the measurement period, and that was due to its lower albedo. Red canopy was about 1 °C warmer than the green canopy on average; however, computer simulation indicates that albedo was of secondary importance in controlling canopy temperature. Contrary to our hypothesis, results suggest that lower stomatal conductance in the red leaves was the main driver of canopy temperature differences between red and green canopies.

Topological and Spectral Properties of Wavy Zigzag Nanoribbons.

Low-dimensional graphene-based nanomaterials are interesting due to their cutting-edge electronic and magnetic properties. Their large surface area, strong mechanical resistance, and electronic properties have enabled potential pharmaceutical and opto-electronic applications. Graphene nanoribbons (GNRs) are graphene strips of nanometer size possessing zigzag and armchair edge geometries with tunable widths. Despite the recent developments in the characterization, design and synthesis of GNRs, the study of electronic, magnetic and topological properties, GNRs continue to pose a challenge owing to their multidimensionality. In this study, we obtain the topological and electronic properties of a series of wave-like nanoribbons comprising nanographene units with zigzag-shaped edges. The edge partition techniques based on the convex components are employed to compute the mathematical formulae of molecular descriptors for the wave-like zigzag GNRs. We have also obtained the spectral and energetic properties including HOMO-LUMO gaps, bond delocalization energies, resonance energies, 13C NMR and ESR patterns for the GNRs. All of these computations reveal zero to very low HOMO-LUMO gaps that make these nanoribbons potential candidates for topological spintronics.

Dinuclear vs. Mononuclear Copper(II) Coordination Species of Tylosin and Tilmicosin in Non-Aqueous Solutions.

The veterinary 16-membered macrolide antibiotics tylosin (HTyl, 1a) and tilmicosin (HTilm, 1b) react with copper(II) ions in acetone at metal-to-ligand molar ratio of 1:2 to form blue (2) or green (3) metal(II) coordination species, containing nitrate or chloride anions, respectively. The complexation processes and the properties of 2-3 were studied by an assortment of physicochemical techniques (UV-Vis, EPR, NMR, FTIR, elemental analysis). The experimental data revealed that the main portion of copper(II) ions are bound as neutral EPR-silent dinuclear complexes of composition [Cu2(µ-NO3)2L2] (2a-b) and [Cu2(µ-Cl)2Cl2(HL)2] (3a-b), containing impurities of EPR-active mono-species [Cu(NO3)L] (2a'-b') and [CuCl2(HL)] (3a'-b'). The possible structural variants of the dinuclear- and mono-complexes were modeled by the DFT method, and the computed spectroscopic parameters of the optimized constructs were compared to those measured experimentally. Using such a combined approach, the main coordination unit of the macrolides, involved in the complex formation, was defined to be their mycaminosyl substituent, which acts as a terminal ligand in a bidentate mode through the tertiary nitrogen atom and the oxygen from a deprotonated (2) or non-dissociated (3) hydroxyl group, respectively.

Spectral Properties of Stochastic Processes Possessing Finite Propagation Velocity.

This article investigates the spectral structure of the evolution operators associated with the statistical description of stochastic processes possessing finite propagation velocity. Generalized Poisson-Kac processes and Lévy walks are explicitly considered as paradigmatic examples of regular and anomalous dynamics. A generic spectral feature of these processes is the lower boundedness of the real part of the eigenvalue spectrum that corresponds to an upper limit of the spectral dispersion curve, physically expressing the relaxation rate of a disturbance as a function of the wave vector. We also analyze Generalized Poisson-Kac processes possessing a continuum of stochastic states parametrized with respect to the velocity. In this case, there is a critical value for the wave vector, above which the point spectrum ceases to exist, and the relaxation dynamics becomes controlled by the essential part of the spectrum. This model can be extended to the quantum case, and in fact, it represents a simple and clear example of a sub-quantum dynamics with hidden variables.

Nature of Linear Spectral Properties and Fast Electronic Relaxations in Green Fluorescent Pyrrolo[3,4-c]Pyridine Derivative.

The electronic nature of 4-hydroxy-1H-pyrrolo[3,4-c]pyridine-1,3,6(2H,5H)-trione (HPPT) was comprehensively investigated in liquid media at room temperature using steady-state and time-resolved femtosecond transient absorption spectroscopic techniques. The analysis of the linear photophysical and photochemical parameters of HPPT, including steady-state absorption, fluorescence and excitation anisotropy spectra, along with the lifetimes of fluorescence emission and photodecomposition quantum yields, revealed the nature of its large Stokes shift, specific changes in the permanent dipole moments under electronic excitation, weak dipole transitions with partially anisotropic character, and high photostability. Transient absorption spectra of HPPT were obtained with femtosecond resolution and no characteristic solvate relaxation processes in protic (methanol) solvent were revealed. Efficient light amplification (gain) was observed in the fluorescence spectral range of HPPT, but no super-luminescence and lasing phenomena were detected. The electronic structure of HPPT was also analyzed with quantum-chemical calculations using a DFT/B3LYP method and good agreement with experimental data was shown. The development and investigation of new pyrrolo[3,4-c]pyridine derivatives are important due to their promising fluorescent properties and potential for use in physiological applications.

Simple Models to Study Spectral Properties of Microbial and Animal Rhodopsins: Evaluation of the Electrostatic Effect of Charged and Polar Residues on the First Absorption Band Maxima.

A typical feature of proteins from the rhodopsin family is the sensitivity of their absorption band maximum to protein amino acid composition. For this reason, studies of these proteins often require methodologies that determine spectral shift caused by amino acid substitutions. Generally, quantum mechanics/molecular mechanics models allow for the calculation of a substitution-induced spectral shift with high accuracy, but their application is not always easy and requires special knowledge. In the present study, we propose simple models that allow us to estimate the direct effect of a charged or polar residue substitution without extensive calculations using only rhodopsin three-dimensional structure and plots or tables that are provided in this article. The models are based on absorption maximum values calculated at the SORCI+Q level of theory for cis- and trans-forms of retinal protonated Schiff base in an external electrostatic field of charges and dipoles. Each value corresponds to a certain position of a charged or polar residue relative to the retinal chromophore. The proposed approach was evaluated against an example set consisting of twelve bovine rhodopsin and sodium pumping rhodopsin mutants. The limits of the applicability of the models are also discussed. The results of our study can be useful for the interpretation of experimental data and for the rational design of rhodopsins with required spectral properties.

Synthesis and Spectral Characteristics of BODIPY Dyes with Two or Three Dipyrrin Domains.

Several boron-dipyrrin (BODIPY) based fluorophores with two and three dipyrrin cores were synthesized and investigated in solvents under the concentration variation. Comparative analysis of spectral and photophysical changes under increasing the number of the cores in the dye molecule was made. Mutual influence of dipyrrin cores was detected leading to the increasing of the compounds rigidity and, thus, the absence of fluorescent molecular rotor effects under the viscosity variation. Aggregation induced quenching, which was observed for many mono-domain BODIPY dyes is reduced in case of investigated poly-domain compounds.

Conformers, properties, and docking mechanism of the anticancer drug docetaxel: DFT and molecular dynamics studies.

The conformational structures and properties of the anticancer drug docetaxel (DTX) are studied theoretically. A total of 3888 trial structures were initially generated by all combinations of internal single-bond rotamers and screened with the B3LYP/3-21G* method. A total of 31 unique conformers were further optimized at the B3LYP/6-311G* method. Their relative energies, dipole moments, rotational constants, and harmonic vibrational frequencies were predicted. Single-point relative energies were then determined at the M06-L/6-311G(2df,p) level. The UV spectrum of the lowest-lying DTX conformer in methanol was investigated with the TD-CAM-B3LYP/6-311 + G(2df,p) method. The 31 unique DTX structures are mainly docked at three different sites within ß-tubulin. Based on the results of molecular docking and double-float MD simulations, the lowest-lying DTX conformer consistently exhibits good docking performance with ß-tubulin. We identified the residues LYS299, ARG215, GLN294, LEU275, THR216, GLU290, PRO274, and THR276 on ß-tubulin as active sites forming a binding pocket responsible for locking DTX within ß-tubulin to make the combination more stable. The RMSD values show that the predicted complexes are favorable, and the SASA analysis shows that the hydrophilic properties of DTX are better than paclitaxel. © 2018 Wiley Periodicals, Inc.

Synthesis and Photochemical Properties of 2,3;5,6-bis(cyclohexano)-BODIPY.

The boron-dipyrromethene (BODIPY) dye containing an annelated cyclohexyl rings at the 2,3 and 5,6-positions of pyrroles has been synthesized and characterized. Photochemical properties of the obtained compound have been investigated in different individual solvents. 2,3;5,6-Bis(cyclohexano)-BODIPY exhibits intense chromophore properties with maximum of S o → S 1 band in the 543-549 nm (A from 66000 to 96000 L/mol·cm). The complex is a fluorophore with a quantum yield up to ~ 100%. The influence of solvent polarity on the spectral properties was evaluated. To better understand the spectroscopic results, quantum chemical calculations were carried out. Photostability of dye was studied.Graphical Abstract.

Gene cloning, characterization, and cytotoxic activity of methionine γ-lyase from Clostridium novyi.

The exploitation of methionine-depleting enzyme methionine γ-lyase (MGL) is a promising strategy against specific cancer cells that are strongly dependent on methionine. To identify MGL from different sources with high catalytic activity and efficient anticancer action, we have expressed and characterized MGL from Clostridium novyi and compared its catalytic efficiency with the previously studied MGL from Citrobacter freundii. The purified recombinant MGL exhibits kcat and kcat /Km for methionine γ-elimination reaction that are 2.4- and 1.36-fold higher than C. freundii enzyme, respectively, whereas absorption, fluorescence, and circular dichroism spectra are very similar, as expected on the basis of 87% sequence identity and high conservation of active site residues. The reactivity of cysteine residues with DTNB and iodoacetamide was investigated as well as the impact of their chemical modification on catalytic activity. This information is relevant because for increasing bioavailability and reducing immunogenity, MGL should be decorated with polyethylene glycol (PEG). It was found that Cys118 is a faster reacting residue, which results in a significant decrease in the γ-elimination activity. Thus, the protection of Cys118 before conjugation with cysteine-reacting PEG represents a valuable strategy to preserve MGL activity. The anticancer action of C. novyi MGL, evaluated in vitro against prostate (PC-3), chronic myelogenous leucemia (K562), and breast (MDA-MB-231 and MCF7) cancer cells, exhibits IC50 of 1.3 U mL-1 , 4.4 U mL-1 , 1.2 U mL-1 , and 3.4 U mL-1 , respectively. A higher cytotoxicity of C. novyi MGL was found against cancer cells with respect to C. freundii MGL, with the exception of PC-3, where a lower cytotoxicity was observed. © 2017 IUBMB Life, 69(9):668-676, 2017.

Leaf aging of Amazonian canopy trees as revealed by spectral and physiochemical measurements.

Leaf aging is a fundamental driver of changes in leaf traits, thereby regulating ecosystem processes and remotely sensed canopy dynamics. We explore leaf reflectance as a tool to monitor leaf age and develop a spectra-based partial least squares regression (PLSR) model to predict age using data from a phenological study of 1099 leaves from 12 lowland Amazonian canopy trees in southern Peru. Results demonstrated monotonic decreases in leaf water (LWC) and phosphorus (Pmass ) contents and an increase in leaf mass per unit area (LMA) with age across trees; leaf nitrogen (Nmass ) and carbon (Cmass ) contents showed monotonic but tree-specific age responses. We observed large age-related variation in leaf spectra across trees. A spectra-based model was more accurate in predicting leaf age (R2  = 0.86; percent root mean square error (%RMSE) = 33) compared with trait-based models using single (R2  = 0.07-0.73; %RMSE = 7-38) and multiple (R2  = 0.76; %RMSE = 28) predictors. Spectra- and trait-based models established a physiochemical basis for the spectral age model. Vegetation indices (VIs) including the normalized difference vegetation index (NDVI), enhanced vegetation index 2 (EVI2), normalized difference water index (NDWI) and photosynthetic reflectance index (PRI) were all age-dependent. This study highlights the importance of leaf age as a mediator of leaf traits, provides evidence of age-related leaf reflectance changes that have important impacts on VIs used to monitor canopy dynamics and productivity and proposes a new approach to predicting and monitoring leaf age with important implications for remote sensing.

Structure of the green fluorescent protein NowGFP with an anionic tryptophan-based chromophore.

A green-emitting fluorescent variant, NowGFP, with a tryptophan-based chromophore (Thr65-Trp66-Gly67) was recently developed from the cyan mCerulean by introducing 18 point mutations. NowGFP is characterized by bright green fluorescence at physiological and higher pH and by weak cyan fluorescence at low pH. Illumination with blue light induces irreversible photoconversion of NowGFP from a green-emitting to a cyan-emitting form. Here, the X-ray structures of intact NowGFP at pH 9.0 and pH 4.8 and of its photoconverted variant, NowGFP_conv, are reported at 1.35, 1.18 and 2.5 Šresolution, respectively. The structure of NowGFP at pH 9.0 suggests the anionic state of Trp66 of the chromophore to be the primary cause of its green fluorescence. At both examined pH values Trp66 predominantly adopted a cis conformation; only ∼ 20% of the trans conformation was observed at pH 4.8. It was shown that Lys61, which adopts two distinct pH-dependent conformations, is a key residue playing a central role in chromophore ionization. At high pH the side chain of Lys61 forms two hydrogen bonds, one to the indole N atom of Trp66 and the other to the carboxyl group of the catalytic Glu222, enabling an indirect noncovalent connection between them that in turn promotes Trp66 deprotonation. At low pH, the side chain of Lys61 is directed away from Trp66 and forms a hydrogen bond to Gln207. It has been shown that photoconversion of NowGFP is accompanied by decomposition of Lys61, with a predominant cleavage of its side chain at the C(γ)-C(δ) bond. Lys61, Glu222, Thr203 and Ser205 form a local hydrogen-bond network connected to the indole ring of the chromophore Trp66; mutation of any of these residues dramatically affects the spectral properties of NowGFP. On the other hand, an Ala150Val replacement in the vicinity of the chromophore indole ring resulted in a new advanced variant with a 2.5-fold improved photostability.

Effect of the Ancillary Ligands on the Spectral Properties and G-Quadruplexes DNA Binding Behavior: A Combined Experimental and Theoretical Study.

In an effort to explore the effect of ancillary ligands on the spectral properties and overall G-quadruplex DNA binding behavior, two new ruthenium(II) complexes [Ru(phen)2 (dppzi)](2+) (1) and [Ru(dmp)2 (dppzi)](2+) (2) (phen=1,10-phenanthroline, dmp=2,9-dimethyl-1,10-phenanthroline, dppzi=dipyrido[3,2-a:2',3'-c]phenazine-10,11-imidazole) were prepared. Complex 1 can emit luminescence in the absence and presence of G-quadruplexes DNA. However, with -CH3 substituent on the 2- and 9-positions of the phen ancillary ligand, no detectable luminescence is observed for complex 2 in any organic solvent or in the absence and/or presence of G-quadruplex DNA. Experimental and molecular docking studies indicated that both complexes interacted with the human telomeric repeat AG3(T2AG3)3 (22AG) G-quadruplex with the stoichiometric ratio of 1:1, but the two complexes showed different G-quadruplex DNA binding affinity. Complex 1 binds to the G-quadruplexes DNA more tightly than complex 2 does. Our results demonstrate that methyl groups on the phen ancillary ligand significantly affect the spectral properties and the overall DNA binding behavior of the complexes. Such difference in spectral properties and DNA binding affinities of these two complexes can be reasonably explained by DFT/TD-DFT calculations. This work provides guidance not only on exploring the G-quadruplexes DNA binding behavior of complexes, but also understanding the unique luminescence mechanism.

Preparation of carbon quantum dots based on starch and their spectral properties.

A simple method for the synthesis of water-soluble carbon quantum dots (CQDs) has been developed based on chemical oxidation of starch. The structures and optical properties of the CQDs were characterized by ultraviolet-visible (UV-Vis) spectroscopy, photoluminescence spectroscopy (PL) and transmission electron microscopy. The CQDs were found to emit bright blue fluorescence and disperse uniformly. The effects of ambient temperature, light and pH on the properties of CQDs were studied. The CQDs exhibited good chemical stability, good photostability and pH sensitivity. Furthermore, the interaction between CQDs and bovine serum albumin (BSA) was investigated.

Chemical Behavior and Bioactive Properties of Spinorphin Conjugated to 5,5'-Dimethyl- and 5,5'-Diphenylhydantoin Analogs.

The discovery of new peptides and their derivatives is an outcome of ongoing efforts to identify a peptide with significant biological activity for effective usage as a possible therapeutic agent. Spinorphin peptides have been documented to exhibit numerous applications and features. In this study, biologically active peptide derivatives based on novel peptide analogues of spinorphin conjugated with 5,5'-dimethyl (Dm) and 5,5'-diphenyl (Ph) hydantoin derivatives have been successfully synthesized and characterized. Scanning electron microscopy (SEM) and spectral methods such as UV-Vis, FT-IR (Fourier Transform Infrared Spectroscopy), CD (Circular Dichroism), and fluorimetry were used to characterize the microstructure of the resulting compounds. The results revealed changes in peptide morphology as a result of the restructuring of the aminoacidic sequences and aromatic bonds, which is related to the formation of intermolecular hydrogen bonds between tyrosyl groups and the hydantoin moiety. Electrochemical and fluorescence approaches were used to determine some physicochemical parameters related to the biological behavior of the compounds. The biological properties of the spinorphin derivatives were evaluated in vivo for anticonvulsant activity against the psychomotor seizures at different doses of the studied peptides. Both spinorphin analog peptides with Ph and Dm groups showed activity against all three phases of the seizure in the intravenous Pentylenetetrazole Seizure (ivPTZ) test. This suggests that hydantoin residues do not play a crucial role in the structure of spinorphin compounds and in determining the potency to raise the seizure threshold. On the other hand, analogs with a phenytoin residue are active against the drug-resistant epilepsy test (6-Hz test). In addition, bioactivity analyses revealed that the new peptide analogues have the potential to be used as antimicrobial and antioxidant compounds. These findings suggest promising avenues for further research that may lead to the development of alternative medicines or applications in various fields beyond epilepsy treatment.

A novel hierarchical approach to insight to spectral characteristics in surface water of karst wetlands and estimate its non-optically active parameters using field hyperspectral data.

Wetlands cover only around 6 % of the Earth's land surface, and are recognized as one of the three major ecosystems, alongside forests and oceans. The ecological structure and function of karst wetlands are unique due to the influence of geologic structure. At present, the unclear spectral morphology of surface water in karst wetlands poses a significant challenge in remote sensing estimation of non-optically active water quality parameters (NAWQPs). This study proposed a novel multi-scale spectral morphology feature extraction (MSFE) method to insight to spectral characteristics in surface water of karst wetlands, and further screen the sensitive features of NAWQPs. Then we constructed three remote sensing inversion strategies for NAWQPs (TN, TP, NH3_N, DO), including direct estimation, indirect estimation, and auxiliary estimation. Finally, we constructed a novel pH-based hierarchical analysis framework (pH_HA) to thoroughly explore the influence of alkalinity-biased characteristics of karst water on the spectral domain of NAWQPs and its estimation accuracy using in-situ hyperspectral data, respectively. We found that the spectral characteristics of karst waters at the first reflectance peak (580 nm) differed significantly from other water body types. The MSFE successfully captured the sensitive spectral domains for NAWQPs, and focused on between 500 and 600 nm and 900-960 nm. The sensitive features captured by MSFE improved estimation accuracy of NAWQPs (R2 >0.9). Direct estimation presented more stable performance compared to the auxiliary estimation (average RMSE of 0.366 mg/L), and the auxiliary estimation model further improved the retrieval accuracy of TN compared to direct estimation model (R2 increasing from 0.43 to 0.56). The novel hierarchical framework clearly revealed the notable changes in the sensitive spectral domains of NAWQPs under different pH values, and enabled more precise determination of spectral subdomains of NAWQPs, and identified the optimal spectral features. The pH_HA framework effectively improved the estimation accuracy of NAWQPs (R2 increased from 0.514 to over 0.9), and the estimation accuracies (R2) of four NAWQPs were all more than 0.9 when the pH value was over 8.5. Our works provide an effective approach for monitoring water quality in karst wetlands.

Large scale expression and purification of mouse melanopsin-L in the baculovirus expression system.

Melanopsin is the mammalian photopigment that primarily mediates non-visual photoregulated physiology. So far, this photopigment is poorly characterized with respect to structure and function. Here, we report large-scale production and purification of the intact long isoform of mouse melanopsin (melanopsin-L) using the baculovirus/insect cell expression system. Exploiting the baculoviral GP67 signal peptide, we obtained expression levels that varied between 10-30pmol/10(6)cells, equivalent to 2-5mg/L. This could be further enhanced using DMSO as a chemical chaperone. LC-MS analysis confirmed that full-length melanopsin-L was expressed and demonstrated that the majority of the expressed protein was N-glycosylated at Asn(30) and Asn(34). Other posttranslational modifications were not yet detected. Purification was achieved exploiting a C-terminal deca-histag, realizing a purification factor of several hundred-fold. The final recovery of purified melanopsin-L averaged 2.5% of the starting material. This was mainly due to low extraction yields, probably since most of the protein was present as the apoprotein. The spectral data we obtained agree with an absorbance maximum in the 460-500nm wavelength region and a significant red-shift upon illumination. This is the first report on expression and purification of full length melanopsin-L at a scale that can easily be further amplified.

A linear S-bridged trinuclear cobalt(III) complex with 2-aminobenzenethiol: Synthesis, crystal structure, and spectroscopic characterization.

Treatment of cobalt(II) perchlorate hexahydrate with 2 molar equiv. of 2-aminobenzenethiol (Habt) in acetonitrile afforded a tricationic tricobalt complex, [Co{Co(abt)3}2](ClO4)3·2CH3CN, by aerial oxidation. The molecular structure of the meso (ΔΛ) form of the complex was determined by X-ray crystallography. In the complex cation, the central Co is coordinated by six thiolate groups from two terminal fac(S)-[Co(abt)3] units in an octahedral geometry, forming a linear S-bridged tricobalt structure.