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The asymmetric catalytic synthesis of 1,2-diamines has received considerable interest, especially in the last ten years, due to their presence in biologically active compounds and their applications for the development of synthetic building blocks, chiral ligands and organocatalysts. Synthetic strategies based on C–N bond-forming reactions involve mainly (a) ring opening of aziridines and azabenzonorbornadienes, (b) hydroamination of allylic amines, (c) hydroamination of enamines and (d) diamination of olefins. In the case of C–C bond-forming reactions are included (a) the aza-Mannich reaction of imino esters, imino nitriles, azlactones, isocyano acetates, and isothiocyanates with imines, (b) the aza-Henry reaction of nitroalkanes with imines, (c) imine–imine coupling reactions, and (d) reductive coupling of enamines with imines, and (e) [3+2] cycloaddition with imines. C–H bond forming reactions include hydrogenation of C＝N bonds and C–H amination reactions. Other catalytic methods include desymmetrization reactions of meso-diamines. [ABSTRACT FROM AUTHOR]

A photoinduced EnT-mediated generation of sulfonamidyl radicals has been accomplished using rationally designed iminophenylacetic acid oxime ester reagents under metal-free conditions. This approach offers a mild, regio- and diastereoselective synthesis of N-sulfonyl diamines via diamination of alkenes and (hetero)arenes. [ABSTRACT FROM AUTHOR]

A series of nine new soft salts based on two platinum(II) complexes, namely ([Pt(C^N)(CN)2]−[Pt(C^N)(en)]+) (en = ethane-1,2-diamine), has been developed and synthesized. Their photophysical properties in both solution and the solid state were described. All soft salt complexes exhibit phosphorescence emission with PLQY in the solid state up to 0.36. Most of these materials displayed aggregation-induced emission (AIE) or aggregation-induced emission enhancement (AIEE) in water/DMSO solutions as the water ratio increased. Structure–property relationships were analyzed in relation to emission properties. The presence of the free nitrogen atoms in soft salt complexes with a C^N pyrimidine-based ligand allowed for reversible sensitivity to acidic vapors, resulting in the quenching of phosphorescence emission. Additionally, for selected soft salts, we described reversible vapochromism behaviour, making these new materials interesting for multi-detection purposes in anti-counterfeiting applications. [ABSTRACT FROM AUTHOR]

A bipolar polymer cathode material, containing redox-active azo benzene and diamine moieties, was synthesized for sodium-ion batteries. The n-type azo group and p-type amine group enable a wide cutoff window with an initial capacity of 93 mA h g−1 at 50 mA g−1 and a high voltage plateau at ∼3.3 V. [ABSTRACT FROM AUTHOR]

The preparation of Fe(II) complexes combining monodentate NCX− (X = S or Se) and the tetradentate Schiff base chiral ligands RR-L1 and SS-L1 = (RR- or SS-L1 = 1R,2R or 1S,2S)-N1,N2-bis(pyridin-2-ylmethylen)cyclohexane-1,2-diamine in acetone results in an unexpected reaction. Thus, four enantiomerically pure compounds of formulas [Fe(RR-S-L2)(NCX)2] and [Fe(SS-R-L2)(NCX)2] (X = S or Se) are formed by the new asymmetrical ligand L2. In L2, one acetone solvent molecule is incorporated into the ligand forming a bond with the C atom of one of the two CN imine groups of L1, which is transformed into an amine (Mannich reaction). This reaction is diastereoselective as the incorporation of acetone leads to an asymmetric C adjacent to the NH group with opposite chirality S- or R- to that of the cyclohexane carbons (RR- or SS-, respectively). Therefore, L2 contains three C chiral centers. Structural and magnetic characterization of these compounds demonstrates that they show in the bulk a gradual spin-crossover behavior and LIESST effect. Interestingly, the presence of an intramolecular hydrogen bond between the integrated acetone molecule and the NH group can trigger a secondary stimuli-responsive behavior in the system. Therefore, by changing the solvent polarity, the color of the complex in solution can be easily tuned. [ABSTRACT FROM AUTHOR]

The chemoselective N-H insertion of unsymmetrical diamines into carbene is a longstanding challenge. A simple copper-catalyzed strategy for synthesizing C-substituted piperazinones is described, employing easily accessible diazo compounds and 1,2-diamines. The reaction proceeded via chemo-selective carbene insertion at the comparatively less nucleophilic amine, followed by instantaneous cyclization. The protocol was further extended to access NH-free piperazinone, and the synthesis of a Mianserin derivative. [ABSTRACT FROM AUTHOR]

Although silane diamine copolymers have captured the attention of the catalysis community, the optimization of their synthesis and end uses have yet to be explored. In this study, a well-defined Earth-abundant metal catalyst, [(2,6-iPr2PhBDI)Mn(μ-H)]2, has been found to couple organosilanes to diamines to prepare networks that feature varied silane substitution and diamine chain lengths. By performing dehydrocoupling in the absence of solvent with 0.01 mol% catalyst loading, substrate utilisation turnover frequencies of up to 300 s-1 have been achieved at early reaction times, the highest Si--N dehydrocoupling activity to be observed on a per catalyst basis. These networks have been employed as absorbents for common organic solvents, a property that had not been studied for this class of materials. By incorporating a longchain hydrophobic linker, one network has been found to absorb 7.7x its original mass in THF and recycling has been demonstrated upon solvent removal. Controlling the degree of dehydrocoupling also offered an opportunity to deposit coatings from freshly-prepared silane diamine polymer solutions and monitor their integrity upon curing in air. While uniform and persistent coatings have been obtained from 1,6-diaminohexane derived polymers, the need to prepare dilute solutions that have a short shelf-life and the tackiness associated with extended dry times have been identified as potential limitations. [ABSTRACT FROM AUTHOR]

Applying molecular design to chiral organo-Zn2+ complexes, a new pair of chiral heteroleptic bis-pyrazolonate-Zn2+ enantiomers [Zn(PMBP)2(1R,2R-Chxn)] (R,R-Zn2+ ; HPMBP = 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and 1R,2R-Chxn = (1R,2R)-cyclohexane-1,2-diamine) and [Zn(PMBP)2(1S,2S-Chxn)] (S,S-Zn2+ ; 1S,2S-Chxn = (1S,2S)-cyclohexane-1,2-diamine) have been synthesized and characterized in terms of photophysical and thermodynamic properties. In addition to a small Flack parameter (0.05(3)) associated with the solid-state elucidation of S,S-Zn2+ , the circular dichroism (CD) and circularly polarized light (CPL) spectra for the chiral Zn2+ enantiomers show perfect mirror symmetry, establishing that the enantiopure 1,2-diamines successfully induce the optical isomerism of R,R-Zn2+ and S,S-Zn2+. As a result of the combined strong chiral induction capability of chiral 1,2-diamines and excellent photophysical properties of the pyrazolone ligand (PMBP)−, the two Zn2+ enantiomers exhibit high-quality pure blue fluorescence (ΦPL = 9–10%) and significant CPL activity (‖glum‖ = 0.0065–0.0068). The heteroleptic strategy adopted in this study offers a new route to develop high-performance chiroptical luminophores. [ABSTRACT FROM AUTHOR]

The document is the contents list for the journal "Chemical Communications" published in 2024. It includes articles on various topics such as enantioselective C-H bond functionalization, fluorescent metal nanoclusters, thioesterases for chemoenzymatic synthesis, and more. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document provides a list of articles and authors, allowing library patrons to quickly identify relevant research topics. [Extracted from the article]

A photoredox-catalyzed unsymmetrical diamination of alkenes by using N-aminopyridinium salts and nitriles as the amination reagents has been developed. Various vicinal diamines were obtained in moderate to excellent yields under mild reaction conditions. Furthermore, this protocol could be applied in the late-stage modification of pharmaceuticals and natural products. Preliminary mechanistic studies suggested that this methodology may undergo a radical pathway followed by a Ritter-type reaction. [ABSTRACT FROM AUTHOR]

Au(III) bis(pyrrolide-imine) chelates are emerging as a class of versatile, efficacious metallodrug candidates. Here, we synthesised two enantiopure chiral ligands H2L1 and H2L2 (tetradentate cyclohexane-1,2-diamine-bridged bis(pyrrole-imine) derivatives). Metallation of the ligands with Au(III) afforded the chiral cationic complexes AuL1 and AuL2. The in vitro cytotoxicities of AuL1 and AuL2 determined in the NCI-60 single-dose drug screen were 56.5% and 89.1%, respectively. AuL1 was subsequently selected for a five-dose NCI-60 screen, attaining GI50, IC50, and LC50 values of 4.7, 9.3 and 39.8 μM, respectively. Hierarchical cluster analysis of the NCI-60 data indicated that the profile for AuL1 was similar to that of vinblastine sulfate, a microtubule-targeting vinca alkaloid. Reactions of AuL1 with glutathione (GSH) in vitro confirmed its susceptibility to reduction, Au(III) → Au(I), by intracellular thiols. Because human serum albumin (HSA) is responsible for transporting clinically deployed and investigational drugs, we studied the uptake of AuL1 and AuL2 by HSA to delineate how chirality impacts their protein-binding affinity. Steady-state fluorescence quenching data acquired on the native protein and data from site-specific probes showed that the compounds bind at sites close enough to Trp-214 (subdomain IIA) of HSA to quench the fluorophore. The bimolecular quenching rate constants, Kq, were ca. 102 times higher than the maximum diffusion-controlled collision constant of a biomolecule in water (1010 M−1 s−1), confirming that static fluorescence quenching was the dominant mechanism. The Stern–Volmer constants, KSV, were ∼104 M−1 at 37 °C, while the affinity constants, Ka (37 °C), measured ∼2.1 × 104 M−1 (AuL1) and ∼1.2 × 104 M−1 (AuL2) for enthalpy-driven ligand uptake targeting Sudlow's site I. Although far- and near-UV CD spectroscopy indicated that both complexes minimally perturb the secondary and tertiary structure of HSA, substantial shifts in the CD spectra were recorded for both protein-bound ligands. This study highlights the role of chirality in determining the cytotoxicity profiles and protein binding behaviour of enantiomeric Au(III) chelates. [ABSTRACT FROM AUTHOR]

Salen-based octahedral trans metallo-salen complexes with monodentate co-ligands may exist as several conformational isomers, including stepped and umbrella shaped conformations. However, the factors governing the selective isolation of a particular conformer have not been investigated properly. In this report, six mononuclear cobalt(III) complexes (1–6) with a tetradentate salen-type Schiff base ligand, N,N′-bis(3-methoxy-5-methylsalicylidene)-ethane-1,2-diamine (H2L), and different heteroaromatic co-ligands (pyridines, imidazole and pyrazole) have been synthesized and characterized to unveil the influence of heteroaromatic co-ligands on the conformational (stepped versus umbrella) selectivity of the resulting complexes. X-ray crystallography reveals that the structures of 1–6 are eventually similar with only differences in the coordinated heteroaromatic moieties at axial positions and the accommodation of a different number of lattice solvent/guest molecules in the crystal voids. Interestingly, although a landscape of intermolecular non-covalent interactions are present in the solid state in these systems, the pyridyl co-ligands exclusively stabilize the umbrella-shaped conformation, while five-membered heteroaromatic bases prefer the stepped-shaped conformation, disclosing that the different degrees of intramolecular interactions (repulsion/attraction) of the six and five membered heteroaromatic ligands at the axial positions play the most important role in the selective stability of the different conformations in the solid state. All these complexes exhibit efficient catalytic activity mimicking the functions of phenoxazinone synthase and catechol oxidase. The catalyst recyclability test was also performed and it showed a very negligible change in catalytic efficiency even after five catalytic cycles. Theoretical calculations were performed to gain in-depth understanding of the preference of pyridine ligands for the umbrella-shaped conformation and the five-membered ring co-ligands for the stepped-shaped one, as well as for the mechanistic investigation of the aerobic oxidation of o-aminophenol in the presence of 1–6 as catalysts. [ABSTRACT FROM AUTHOR]

Many efforts have been made in the last few decades to selectively transport antitumor agents to their potential target sites with the aim to improve efficacy and selectivity. Indeed, this aspect could greatly improve the beneficial effects of a specific anticancer agent especially in the case of orphan tumors like the triple negative breast cancer. A possible strategy relies on utilizing a protective leaving group like alizarin as the Pt(II) ligand to reduce the deactivation processes of the pharmacophore enacted by Pt resistant cancer cells. In this study a new series of neutral mixed-ligand Pt(II) complexes bearing alizarin and a variety of diamine ligands were synthesized and spectroscopically characterized by FT-IR, NMR and UV–Vis analyses. Three Pt(II) compounds, i.e., 2b, 6b and 7b, emerging as different both in terms of structural properties and cytotoxic effects (not effective, 10.49 ± 1.21 μM and 24.5 ± 1.5 μM, respectively), were chosen for a deeper investigation of the ability of alizarin to work as a selective carrier. The study comprises the in vitro cytotoxicity evaluation against triple negative breast cancer cell lines and ESI-MS interaction studies relative to the reaction of the selected Pt(II) complexes with model proteins and DNA fragments, mimicking potential biological targets. The results allow us to suggest the use of complex 6b as a prospective anticancer agent worthy of further investigations. [ABSTRACT FROM AUTHOR]

A novel method for synthesizing biobased diamide tetraol derivatives through mechanochemical processes is presented in this study. The key component used in the synthesis is (S)-γ-hydroxymethyl-γ-butyrolactone (2H-HBO), a cellulose-based lactone derived from levoglucosenone, combined with various linear diamines. The use of planetary ball milling in the presence of a small excess of diamine was found to be crucial for achieving complete conversion of 2H-HBO and the selective formation of diamide tetraol derivatives. The optimized parameters established for the reaction of 2H-HBO using diaminohexane were applied to biobased, non-toxic, and biodegradable diamines such as spermidine, spermine, and 4,9-dioxa-dodecanediamine. This resulted in high conversions and good yields of diamide tetraol derivatives. The scalability of the process was demonstrated by transposing the reaction from 100 mg to 2 g, with improved conversions obtained at a larger scale. The greenness of the procedure was assessed using the E-factor and EcoScale, showing low waste generation and acceptable to excellent reaction conditions. In addition, enzymatic polymerization of diamide tetraol derivatives using CAL-B (Candida antarctica lipase B) as a biocatalyst was explored. Successful polymerization of monomers obtained from hexamethylene diamine and 4,9-dioxa-dodecandiamine was achieved, providing insights into the effect of enzyme loading and monomer ratios on the molecular weight of the resulting polymers. Despite challenges with certain monomers containing amine groups, this work offers a promising approach for producing multifunctional biobased polymers. [ABSTRACT FROM AUTHOR]

Transmetalation plays a very important role in the study of functional MOFs, but it is rarely used in metal–organic salts (MOSs). In this paper, four kinds of MOSs were synthesized by using the tetradentate ligand N,N′-bis (pyridin-4-ylmethyl) ethane-1,2-diamine and MCl2 (M = Zn, Co, Cu), labelled as [H4L]4+·2[CoCl4]2−·2H2O (1), [H4L]4+·2[ZnCl4]2−·2H2O (2), [H4L]4+·[CuCl4]2−·2Cl− (3), and [H4L]4+·2[CuCl4(H2O)]2− (4). Salt 3 was obtained by the metal-ion exchange of salt 1, and salt 4 was successfully synthesized by liquid-assisted grinding (LAG) of salt 3 and CuCl2·2H2O, which was a stoichiometric ratio-controlled transformation that occurred with the change in the geometry of copper(II) anions from [CuCl4]2− and [CuCl4(H2O)]2−. The reaction process was monitored dynamically by atomic absorption spectroscopy (AAS), fluorescence spectroscopy, and powder X-ray diffraction (PXRD). This suggested that transmetalation combined with LAG was an alternative method to obtain MOSs for different metal ions. [ABSTRACT FROM AUTHOR]

The triazolate-assisted asymmetric dinuclear oxovanadium(IV) citrate [V2O2(cit)(Hdatrz)3]·5H2O (1, H4cit = citric acid, Hdatrz = 1H-1,2,4-triazole-3,5-diamine) and its additive salt [V2O2(cit)(Hdatrz)3][V2O2(cit)2]½·2H2datrz·9.5H2O (2) and the polymerized hexanuclear product [V6O6(μ3-O)2(cit)2(Hdatrz)4]·4H2O (3) have been isolated at different temperatures, respectively. Adduct 2 shows strong evidence for the conversion of a symmetric dinuclear oxovanadium(IV) citrate to a mixed-ligand asymmetric oxovanadium(IV) citrate. Moreover, a fully oxidized trinuclear vanadium(V) species [V3O6(μ2-OH)(μ3-O)(Hdatrz)2]·4.5H2O (4) has also been isolated as a quasi-intermediate product of 3 without the coordination of citrate. Intriguingly, an octanuclear mixed-valence oxovanadium(V / IV) citrate K2{[V IV/V2 O2(cit)(Hdatrz)(datrz)]2[V IV2 O2(cit)(Hdatrz)(datrz)]2}·27.5H2O (5) has been obtained with different vanadium units, where dinuclear mixed-ligands and mixed-valence oxovanadium(IV / V) citrates [V IV/V2 O2(cit)(Hdatrz)(datrz)] (5a) and [V IV2 O2(cit)(Hdatrz)(datrz)] (5b) have been trapped. Citrate adopts a μ2-η1:η1:η1:η2 coordination mode in 1, 2 and 5, while a μ3-η1:η1:η1:η2 fashion has been observed in 3. Unlike 1–4, complex 5 contains both protonated and deprotonated triazolates simultaneously, where four triazolates further coordinate in a μ3-η1:η1:η1 manner to construct an octanuclear unit. These different structural features in 1–5 are dominated by flexible multidentate citrates and protonated/deprotonated triazolates, showing their synergistic effects. Furthermore, 1 exhibits a rectangular channel, showing preferential adsorption of O2 and CO2 over gases N2, H2, and CH4. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Green Chemistry," published by The Royal Society of Chemistry. It highlights various articles and papers featured in the journal's latest issue, covering topics such as sustainable chemistry, electrocatalysis, and environmentally friendly synthesis methods. The journal aims to promote research for a greener and more sustainable future. [Extracted from the article]

2,3-Diamines are skeleton structures widely found in natural products and drug molecules and can also be used as ligands in transition metal catalysis. A novel visible light-driven synthesis method for 2,3-diamines using anilines and diisopropylethylamine as starting materials and aldehydes as proton acceptors under the action of the organic photosensitiser 4CzIPN has been developed. The method has mild conditions, avoids the use of metal reagents and the reaction mechanism does not involve the imine intermediate. Under optimal conditions, the yield of 2,3-diamines is up to 90%. In addition, the aldehydes give rise to 2,3-diols after the reaction, which means that the method can synthesise diamines and diols in one pot. [ABSTRACT FROM AUTHOR]

The N-formylation and N-methylation of amines with carbon dioxide (CO2) are important types of transformations which give access to a wide range of key intermediates and compounds. Efficient catalytic methods for both reactions are rare because of the challenge of controlling selectivity. Herein, we report the environmentally benign organocatalyzed N-formylation and N-methylation of primary and secondary amines using CO2 as the C1 source in the presence of hydrosilanes as the reductant. Readily available methyltriphenylphosphonium methylcarbonate has been proven to be an efficient catalyst for the N-methylation of amines and CO2 in the presence of polymethylhydrosiloxane (PMHS) under mild conditions. In contrast, the selective N-formylation is achieved in the presence of trimethoxysilane as the reductant. In both transformations, a wide range of substrates were selectively converted. 15 primary and secondary amines were N-methylated and N-formylated and the corresponding products were obtained in yields of up to 98% and 94%, respectively. Moreover, benzimidazoles are accessible from diamines and CO2 in a one-pot reaction in yields of up to 83%. Mechanistic investigations revealed different reaction pathways for N-methylation and N-formylation depending on the reductant as well as the activation of CO2 by the catalyst. [ABSTRACT FROM AUTHOR]

The reaction of (1R,2R)-(cyclohexane-1,2-diamine)dichloridoplatinum(II) with maleic acid unexpectedly resulted in the formation of an organometallic platinum(II) complex featuring a C,O-coordinating ligand. Additionally, a small series of close derivatives with increasing lipophilicity was synthesized. All complexes were fully characterized by multinuclear one- and two-dimensional (1H, 13C, 15N, and 195Pt) NMR spectroscopy, high resolution mass spectrometry, and in one case by X-ray diffraction. The lipophilicity and the impact on the DNA secondary structure as well as the cytotoxic properties in three human cancer cell lines (A549, SW480, and CH1/PA-1) were investigated. Unexpectedly, no clear-cut trend in cytotoxicity was observed with increasing lipophilicity. Also unexpectedly, the complexes showed only a low potential to inhibit cancer cell growth and no sign of interaction with DNA, in sharp contrast to the parent drug oxaliplatin, which seems to be caused by the low reactivity of the investigated compounds. [ABSTRACT FROM AUTHOR]

Bis(bidentate) and bis(tridentate) Co(III) complexes of N-(2-hydroxyethyl)ethane-1,2-diamine (heen), 2-[(2-aminoethyl)amino]ethan-1-olate (heen-H), or N-(2-chloroethyl)ethane-1,2-diamine (ceen) ligands have been synthesised, and a range of reaction conditions established for their syntheses by different routes. They can all be ultimately derived from (OC-6-12′)-[Co(heen)2(NO2)2]NO3 and provide access to the trans amine trans chloride nitrogen mustard complex, (OC-6-12′)-[Co(ceen)2(Cl)2]Cl. Although complex isomeric mixtures were obtained from the reaction of (OC-6-12′)-[Co(heen)2(NO2)2]NO3 under different reaction conditions, ultimately, the trans amine trans chlorido configuration around the Co(III) metal centre of the (OC-6-12′)-[Co(ceen)2(Cl)2]Cl complex was favoured. [ABSTRACT FROM AUTHOR]

Optically active C2-symmetric bis(aminophenols) based on (R)-2,2′-diaminobinaphthyl (BiniqH4) and (R,R)-2,3-butanediyldianthranilate (BdanH4) have been prepared by condensation of the diamines with 3,5-di-tert-butylcatechol. Group 10 bis(iminosemiquinone) complexes (R)-(Biniq)M (M = Pd, Pt) and (C,R,R)-(Bdan)Pd have been prepared by oxidatively metalating the corresponding ligands. In (R)-(Biniq)M, the C2 axis passes through the approximate square plane of the bis(iminosemiquinone)metal core, while in (C,R,R)-(Bdan)Pd the C2 axis is perpendicular to this plane. In the latter compound, the (R,R)-butanediyl strap binds selectively over one enantioface of the metal complex in a conformation where the methyl groups are anti to one another. Osmium oxo complexes with the intrinsically chiral OsO(amidophenoxide)2 chromophore are obtained by metalation of OsO(OCH2CH2O)2 with (R,R)-BdanH4. Both the (A,R,R) and (C,R,R) diastereomers can be observed, with metalation in refluxing toluene selectively giving the latter isomer. The electronic structures of the complexes are illuminated by the circular dichroism spectra, in conjuction with the optical spectra and TDDFT calculations. [ABSTRACT FROM AUTHOR]

A series of viscosity probes targeting different organelles were obtained using a single hemicyanine dye as the matrix structure. Specifically, probes 1a–d were obtained by introducing four amines (6-amino-2H-chromen-2-one, N-(2-aminoethyl)-4-methylbenzenesulfonamide, dodecan-1-amine and N,N diphenylbenzene-1,4-diamine) into the indole hemicyanine dye of the carboxylic acid with a D–π-A structure. Their maximum absorption wavelengths were in the range 570–586 nm and they had relatively large molar absorption coefficients, while their maximum emission wavelengths in the red light region were in the range 596–611 nm. Moreover, their fluorescence intensity in glycerol was 35–184 times higher than that in phosphate buffer solution (PBS). The lg(Fl) and lg η of probes 1a–d showed good linearity with high correlation coefficients according to the Förster–Hoffman equation. In addition, cell staining experiments demonstrated that 1a–c could target lysosomes, endoplasmic reticulum and mitochondria, respectively. They could also undergo viscosity-detectable changes in the corresponding organelles under the action of the corresponding ion carriers. [ABSTRACT FROM AUTHOR]

The reaction of [(Me/BnTPEN)RuII(NCCH3)]2+ (BnTPEN = N1-benzyl-N1,N2,N2-tris(pyridine-2-ylmethyl)ethane-1,2-diamine and MeTPEN = N1-methyl-N1,N2,N2-tris(pyridine-2-ylmethyl)ethane-1,2-diamine) with mCPBA in the presence of chloride ions in CH3CN : H2O generated a novel (Me/BnTPEN)RuIII–OCl species at room temperature. This hypochlorite adduct could also be obtained by the direct reaction of NaOCl and HClO4 with (L)RuII complexes. The current study mimics the synthesis of a metal hypochlorite adduct in a similar fashion as in the heme-dependent haloperoxidase enzyme. As an electrophilic oxidant, the ruthenium hypochlorite adduct catalyzes hydrogen atom abstraction reactions of phenols and their derivatives. [ABSTRACT FROM AUTHOR]

Volatile organic compounds (VOCs) continue to be one of the biggest problems for air quality and it is becoming increasingly urgent to find new systems capable of limiting their concentration in the atmosphere. Thanks to their capacity to recognize halogenated derivatives, Pillar[5]arenes were used to form high performance thermosets able to absorb chlorine and bromide-based VOCs. Initially, poly(2-vinyl-4,4-dimethylazlactone) featuring different chain length were synthetized and modified by ring opening reaction by mono-amino substituted P[5]A. The high-Tg polymers obtained were then crooslinked by isophore diamine to form high performance materials featuring Tg up to 150 °C and storac modulus G′ up to 85 MPa. The ability of P[5]A cavities to capt VOCs was investigated by vapor sorption tests in presence of dichloromethane, 1,2-dibromoethane, dibromochloromethane and 1,1,2,2-tetrachloroethane. The P[5]A-based thermosets shown to be efficient to absord these carcenogenic VOCs and, this efficiency depends on the affinity of cavities for the studied VOCs, proving that these new generation of thermosets seems to be selective towards certain VOCs. [ABSTRACT FROM AUTHOR]

The complex [PtCl2(cyclohexane-1R,2R-diamine)] has been combined in a Pt(IV) molecule with two different bioactive molecules (i.e., the histone deacetylase inhibitor 2-propylpentanoic acid or valproic acid, VPA, and the potential antimetastatic molecule 4-isopropenylcyclohexene-1-carboxylic acid or perillic acid, PA) in order to obtain a set of multiaction or multitarget antiproliferative agents. In addition to traditional thermal synthetic procedures, microwave-assisted heating was used to speed up their preparation. All Pt(IV) complexes showed antiproliferative activity on four human colon cancer cell lines (namely HCT116, HCT8, RKO and HT29) in the nanomolar range, considerably better than those of [PtCl2(cyclohexane-1R,2R-diamine)], VPA, PA, and the reference drug oxaliplatin. The synthesized complexes showed pro-apoptotic and pro-necrotic effects and the ability to induce cell cycle alterations. Moreover, the downregulation of histone deacetylase activity, leading to an increase in histone H3 and H4 levels, and the antimigratory activity, indicated by the reduction of the levels of matrix metalloproteinases MMP2 and MMP9, demonstrated the multiaction nature of the complexes, which showed biological properties similar to or better than those of VPA and PA, but at lower concentrations, probably due to the lipophilicity of the combo molecule that increases the intracellular concentration of the single components (i.e., [PtCl2(cyclohexane-1R,2R-diamine)], VPA and PA). [ABSTRACT FROM AUTHOR]

The design of heat-resistant energetic compounds generally employs symmetry, planarity, and multi-hydrogen bonds to obtain compounds with high density, good thermal stability, and low sensitivity. In this paper, a heat-resistant hydrazine-bridged compound, 6,6′-(hydrazine-1,2-diyl)bis(5-nitropyrimidine-2,4-diamine) (PHP), was designed and synthesized with the strategy of multi-fused conjugated structure constructed by hydrogen bonds. The compound featured high symmetry, high planarity, and strong conjugation with good thermal stability (364 °C). This strategy provides a basis for the design of heat-resistant energetic compounds. [ABSTRACT FROM AUTHOR]

Highly efficient asymmetric hydrogenation of dibenzo[b,f][1,4]oxazepine, dibenzo[b,f][1,4]thiazepine and dibenzo[b,e]azepine derivatives with chiral cationic ruthenium diamine catalysts has been developed, giving diverse chiral seven-membered N-heterocycles with excellent results (up to 99% yield and 99% ee). Moreover, it was found that the catalyst counteranion regulated the enantioselectivity obviously in the hydrogenation of dibenzo[b,f][1,4]thiazepine and dibenzo[b,e]azepine derivatives. [ABSTRACT FROM AUTHOR]

The initial use of a tetradentate Schiff base (LH2) derived from the 2 : 1 condensation between 2-hydroxyacetophenone and cyclohexane-1,2-diamine in 4f-metal chemistry is described. The 1 : 2 reaction of Ln(NO3)3·xH2O (Ln = lanthanoid or yttrium) and LH2 in MeOH/CH2Cl2 has provided access to isostructural complexes [Ln(NO3)3(L′H2)(MeOH)] in moderate to good yields. Surprisingly, the products contain the corresponding Schiff base ligand L′H2 possessing six aliphatic –CH2– groups instead of the –CH–(CH2)4–CH– unit of the cyclohexane ring, i.e. an unusual ring-opening of the latter has occurred. A mechanism for this LnIII-assisted/promoted LH2 → L′H2 transformation has been proposed assuming transient LnII species and a second LH2 molecule as the H2 source for the reduction of the cyclohexane moiety. DFT calculations provide strong evidence for the great thermodynamic stability of the products in comparison with analogous complexes containing the original intact ligand. The structures of the PrIII, SmIII, GdIII, TbIII, and HoIII complexes have been determined by single-crystal X-ray crystallography. The 9-coordinate LnIII centre in the molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the bidentate chelating organic ligand, and one oxygen atom from the coordinated MeOH group. In the overall neutral bis(zwitterionic) L′H2 ligand, the acidic H atoms are clearly located on the imino nitrogen atoms and this results in the formation of an unusual 16-membered chelating ring. The coordination polyhedra defined by the nine donor atoms around the 4f-metal-ion centres can be best described as distorted, spherical capped square antiprisms. The EuIII, TbIII, and DyIII complexes exhibit LnIII-based luminescence in the visible region, with the coordinated L′H2 molecule acting as the antenna. Ac magnetometry experiments show that the DyIII member of the family behaves as an SIM at zero field and under external dc fields of 0.1 and 0.2 T without the enhancement of the peaks' maxima, suggesting that QTM is not the relaxation path. The GdIII complex behaves, rather unexpectedly, as a SIM with two different magnetic relaxation paths occurring at very close temperatures; this behaviour is tentatively attributed to a very small axial zero-field splitting (D ∼ 0.1 cm−1), which cannot be detected by magnetization or susceptibility experiments. The prospects of the present, first results in the lanthanoid(III)-LH2 chemistry are discussed. [ABSTRACT FROM AUTHOR]

In this manuscript we report the preparation of four new zinc complexes, [{(μ-CH3COO)ZnL1}2Zn]·2DMSO (1), [{(DMF)ZnL1(μ-CH3COO)ZnL1Zn(N3)}]·0.64DMSO·0.36EtOH (2), [(μ-CH3COO)2Zn2L1]n(3) and [Zn2L2Cl2] (4), and their characterization by elemental and spectral analyses, where H2L1 is 1,3-propanediylbis(iminomethylene)bis(4-chlorophenol) and H2L2 is 1,3-propanediylbis(iminomethylene)bis(6-methoxyphenol). The structures have been confirmed by single crystal X-ray diffraction analysis. The synthetic strategy for complexes 1 and 2 involves the use of drops of DMSO, which is essential to stabilize the crystals of 1 and 2, respectively, indicating the importance of DMSO in the stabilization of the complexes. A thorough DFT calculation using the quantum theory of atoms-in-molecules and the non-covalent interaction plot (NCI plot) indicates the formation of strong H-bonds, CH⋯π and ancillary SpBs in complexes 1 and 2. DMSO has not been added during the synthesis of complexes 3 and 4, where no spodium bonds have been observed. Strong self-assembled (π–π stacked or H-bonded) dimers have been found in the solid state structures of 3 and 4. [ABSTRACT FROM AUTHOR]

Perovskite solar cell (PSC) commercialization faces intrinsic stability and efficiency challenges. N1-phenylethane-1,2-diamine hydrohalides (PNEAX) based on a new design strategy featuring cation and anion optimization have been developed for efficient interfacial passivation. Among them, PNEACl-treated devices achieved a champion efficiency of 21.01% with good stability. [ABSTRACT FROM AUTHOR]

The synthesis of a new porous organic cage decorated with isopropyl moieties (CC21) was achieved from the reaction of triformylbenzene and an isopropyl functionalised diamine. Unlike structurally analogous porous organic cages, its synthesis proved challenging due to competitive aminal formation, rationalised using control experiments and computational modelling. The use of an additional amine was found to increase conversion to the desired cage. [ABSTRACT FROM AUTHOR]

Considering the structural design of some of the scarce molecular-based Er-centred emitters in the literature, we explored the optical properties of three ErIII hexaazamacrocyclic complexes, namely Er-EDA (1), Er-OPDA(2) and Er-DAP(3). The macrocyclic ligands in these complexes differ in the lateral spacers, and are derived from 2,6-pyridine-dicarbaldehyde and ethylenediamine (EDA), ortho-phenylenediamine (OPDA) or 1,3-diaminopropane (DAP). Upon ligand-centred excitation, the bluish-green and green emissions of the ErIII ion were detected only for the complexes containing macrocycles with aliphatic spacers (1 and 3), which evidenced that these ligands can sensitize the ErIII luminescence. On the other hand, the ligand derived from the aromatic diamine (2) does not sensitize the ErIII luminescence. Energy transfer mechanisms, temperature sensing, CIE coordinates and CCT values were analyzed. Besides the excitation in the ligands, the erbium-centred excitation at 980 nm allowed the detection, in all cases, of bluishgreen, green and red up-converted emissions, and also the downshifted NIR emission. The possible mechanisms involved in these transitions were described and analyzed according to the available data. [ABSTRACT FROM AUTHOR]

Here we report a theoretical-experimental study of 4,5,6,7-tetrahydrobenzo[d]thiazole-2,6-diamine derivatives that act as inhibitors of bacterial DNA gyrase B (GyrB). A comprehensive analysis of the various molecular interactions that stabilize the molecular complexes was performed using combined theoretical techniques. Our results showed that QTAIM (Quantum Theory of Atoms In Molecules) calculations are a very useful tool for quantitatively describing the molecular interactions to determine which amino acids interact with the ligands. Moreover, our simulations have shown that this approach not only provides a detailed description of the different affinities of the ligands, but also has predictive power for compounds that have not yet been synthesized. In fact, we have synthesized and tested three new DNA gyrase inhibitors, two of which exhibit significant inhibitory activity. One of them binds spatially differently from known GyrB inhibitors because its 3-oxopropanoic acid moiety is oriented toward a previously unexplored subsite of the binding pocket. [ABSTRACT FROM AUTHOR]

Diamides are ubiquitous in chemical structures of organic molecules with a variety of applications. Most of these diamides are accessed via acylation of diamines with corresponding acyl donors, using a protecting group, or with excess amounts of diamines to prevent unwanted diacylation reactions. Here we report a practical and atom-economical method to access monoamide and unsymmetric diamides with diamines and stoichiometric amounts of acyl chlorides – the most accessible and highly reactive acyl donor. The reactivity of diamines can be controlled by CO2 as a green, temporary and traceless protecting group for monoacylation reactions, achieving high atom efficienty and low environmental factor. We demonstrated the utility of the method with a broad substrate scope and a large scale reaction, and performed control experiments to elucidate the origin of the high selectivity obtained with CO2. We showed that ambient CO2 from thin air affected the selectivity of monoacylation of diamines, implying the pervasive influence of atmospheric CO2 in organic synthesis. [ABSTRACT FROM AUTHOR]

Two polymorphs, α (Z′ = 4) and β (Z′ = 1), of an N2,6-diaryl-1,3,5-triazine-2,4-diamine derivative have been isolated at different times from ethanol solution. Significant conformational variability in the five independent molecules is apparent. The molecular packing is distinct but features some commonalties such as the formation of eight-membered {⋯HNCN}2 synthons mediated by phenylamino-N–H⋯N(triazine) hydrogen bonds and (external) supporting amino-N–H⋯C(phenylamino) contacts. The dimeric aggregates are connected into two-dimensional arrays via triazine-amino-N–H⋯O(methoxy) hydrogen bonds. In each crystal, the interactions involve chemically equivalent triazine-N, methoxy-O and amino-H atoms. However, the connections between layers is distinct, notably with superimposition of pairs of molecules via π⋯π stacking between all three aromatic rings in the α-form being restricted to π⋯π stacking between triazine rings only in the β-form. The experimental molecular structures have been subjected to a conformational analysis and compared to the geometry-optimised molecule. The MEP and NPA have been evaluated, and the molecular packing investigated by the analysis of the calculated Hirshfeld surfaces, interaction energies, NCI plots and energy frameworks. The kinetic α-polymorph crystallises with Z′ = 4 and features expansive, stabilising π⋯π interactions in the molecular packing which is achieved by relatively unstable conformations of three of the four molecules. The α-polymorph is readily converted to the thermodynamic β-polymorph, which has the most stable molecular conformation, in solution, with the egress of time, and in the solid-state via heating of single crystals and powdered samples. The adoption of the crystal form results from an interplay between global molecular packing and stability of molecular conformation. [ABSTRACT FROM AUTHOR]

We report a new approach that allows highly efficient one-step conversion biomass-derived carbohydrates to high-value 2-methylquinoxalines in the presence of aryl-1,2-diamines in water at room temperature and under ambient pressure. A joint effect from ultrasound and strong alkali is revealed as the key for enabling this transformation. Various carbohydrates and diverse aryl-1,2-diamines verified the efficient and selective production of various 2-methylquinoxalines (up to 83 C% yield) under mild conditions. More importantly, a novel integrated chemo-enzymatic process, based on the enzymatic catalytic degradation of cellulose and ultrasound-enabled chemical transformation of glucose, is proposed for the direct conversion of recalcitrant cellulose to 2-methylquinoxalines under near room-temperature conditions. [ABSTRACT FROM AUTHOR]

A multienzymatic cascade for the synthesis of 1,6-hexamethylenediamine (HMD) and related α,ω-diamines from corresponding cycloalkanols is reported herein. In this work, an E coli-based modularization strategy was applied to distribute the complete biosynthetic pathway into different modules. The engineered transaminase variant SPTA_R417F has a beneficial impact on the cascade by driving the reaction towards target product formation. This new variant has lost >95% activity towards detrimental pyruvate, generated via auxiliary intracellular glucose metabolism in a host cell. The designed E. coli consortium including respective modules has produced 42% of HMD (from 10 mM cyclohexanol) in a one-pot-one-step manner. This developed route is the first example of a biocatalytic synthesis of HMD and related α,ω-diamines from corresponding cycloalkanols by employing E. coli-based consortia. [ABSTRACT FROM AUTHOR]

The stereocontrolled synthesis of complex spirotricyclic systems containing an embedded syn-1,2-diaminocyclohexane unit is reported, based upon a dearomatising oxidation of phenols bearing pendant ureas capable of acting as double nucleophiles. This complexity-generating transformation yields products with rich functionality suitable for application in the synthesis of potentially bioactive compounds. [ABSTRACT FROM AUTHOR]

Vicinal diamines are an important structural motif in bioactive natural products and pharmaceutical intermediates. Herein, an environmentally friendly and efficient electrochemical approach to azidoacetamides, as one variant of vicinal diamines, has been developed. This reaction features mild conditions and broad substrate scope, without the use of any chemical oxidant or transition-metal catalysts. The obtained vicinal azidoacetamides could be conveniently converted into various other vicinal diamine derivatives. [ABSTRACT FROM AUTHOR]

Quaterphenyl-5′-carbaldehyde 1 with metal ion coordination ability was synthesized for the first time and used for chiral analyte-binding and chiroptical sensing. The formation of an imine between 1 and amine analytes, such as alcohol amines, diamines, and amino acids, enabled Zn(II)-assisted chiral transfer from the analyte to the atropisomeric biphenyl unit, thereby amplifying the circular dichroism (CD) signal, leading to discernible Cotton effects in the range of 350–450 nm, with g values on the order of magnitude of 10−3 in MeOH. Linear relationships between the CD amplitude and enantiomer excess (ee) of the analytes were observed, enabling use of 1 as a chiroptical probe for amines. Interestingly, 1 showed a fluorescence response to change in concentrations of L -phenylalaninol ((S)-G1) in the presence of Zn(II) upon excitation at 380 nm. It suggests that 1 could serve as a dual chemosensor for the determination of both the ee and concentration of analytes. The Zn(II)-assisted fluorescence behavior was also subjected to circular polarization luminescence (CPL) measurements. [ABSTRACT FROM AUTHOR]

In this communication, a PdMn bimetallene is synthesized using a template-free solvothermal method with the assistance of diamines. The PdMn bimetallene with rich defects and highly curved structures shows superior performance for the formate oxidation reaction (FOR) and the hydrogen evolution reaction (HER). For the two-electrode HER–FOR system, the PdMn bimetallene achieves a much lower voltage of 0.376 V at 10 mA cm−2, demonstrating an energy-effective path for hydrogen production. [ABSTRACT FROM AUTHOR]

In this work, a simple and stepwise strategy has been adopted for the successful synthesis of diamine functionalized porous graphene oxide sheets decorated with ultra-small palladium oxide nanoparticles. The successful synthesis, stepwise functionalization, morphology and elemental composition have been authenticated by using numerous physicochemical characterization techniques such as FT-IR, TGA, powder XRD, SEM, HR-TEM, EDAX, elemental mapping, CHNS, ICP-MS and XPS analyses. The prepared nano-catalyst has been employed as a recyclable catalyst for the oxidative amidation of aldehydes with amines. The main features of this nano-catalyst include mild reaction conditions, simple work-up procedure, high product yield without any hazardous by-products and recyclability for several catalytic cycles. It could be believed that the unique porous architecture of the nano-catalyst was responsible for the enhanced specific surface area which favors a quick response and improved interaction between the catalytic active moieties and the reactants. [ABSTRACT FROM AUTHOR]

A one-step condensation procedure in the presence of green solvent EtOH was used to make a pyrene-based fluorescent sensor (PNPD). It could be used as a rapid, low-cost, selective, and sensitive chemodosimetric probe to detect water content. PNPD showed a cyan-blue emission in the presence of water due to cleavage of the imine bond, thus giving back the emission of pyrene carboxaldehyde. It displayed a relative error percentage of less than x ± 0.5% for the percentage detection of water content with noticeable DL and QL as compared to the reported works. A normalised approach was also developed to address the lack of knowledge in the quantitative detection of water content in an unknown sample. This approach can be used with any solvents and instruments, making it a quick, cost-effective, sensitive, and selective water sensing technique. The findings revealed that PNPD can detect water in polar, non-polar, protic, and aprotic solvents, with the detection limit and quantitation limit preferring polar aprotic solvent ACN and dioxane in both higher and lower water content. Also, we have developed a method for quantitative detection of water content in organic solvents by fluorescence studies. The real-time applicability of PNPD has been analysed by taking honey as an example, and a detection limit of 0.206 v% and quantitation limit of 0.624 v% have been found. [ABSTRACT FROM AUTHOR]

The synthesis of a range of N-(heterocyclesulfonyl)-functionalised Noyori–Ikariya catalysts is described. The complexes were prepared through a short sequence from C2-symmetric 1,2-diphenylethylene-1,2-diamine (DPEN) and were characterised by a range of methods including X-ray crystallography. The complexes were active catalysts for the asymmetric transfer hydrogenation (ATH) of a range of acetophenone derivatives, giving products of high ee in most cases, with notably good results for ortho-substituted acetophenones. [ABSTRACT FROM AUTHOR]

In order to make recycling a viable strategy for post-consumer plastics, economically feasible revalorization processes must be developed. The ammonolysis of polyamides can be such a cutting-edge recycling technology; however, due to the rigid structure of these polyamide plastics, operating conditions of current ammonolysis processes are harsh, including high temperatures (>300 °C) and high NH3 pressures. Here, we report a very green and elegant ammonolysis process of the widely abundant polyamide 66 by using a hard Lewis acid catalyst and 1 bar of NH3 in a simple glycol solvent at 200 °C. Computational studies revealed that especially the vicinal diol moiety of these glycol solvents plays a key role in activation of the ammonia nucleophile, with glycerol being the most effective solvent, reaching the depolymerization equilibrium after 20 h even without a catalyst. To our delight, a biosourced glycerol (obtained from the saponification of triglycerides) could also directly serve as a suitable solvent, even outperforming the ammonolysis process in highly purified glycerol. [ABSTRACT FROM AUTHOR]

Recently, waste biomass-derived catalysts have emerged as sustainable and remarkable alternatives to petroleum (depleting resource)-based catalysts. We report here the application of a water extract of pomegranate peel ash (WEPA) as an effective catalyst in an aqueous medium for the construction of quinoxalines from aryl/heteroaryl 1,2-diamines and α-hydroxy ketones via a metal catalyst/added oxidant-free sequential condensation–cyclization–oxidation process with a sensible mechanism. The catalyst was systematically characterized using inductively coupled plasma mass spectrometry (ICP-MS), energy dispersive X-ray fluorescence (ED-XRF), Fourier transform infrared (FT-IR), powder X-ray diffraction (XRD), scanning electron microscopy(SEM), energy-dispersive X-ray spectroscopy (XEDS) and microwave plasma atomic emission spectroscopy (MP-AES) data. The quinoxalines were purified by recrystallization with excellent yields. The developed process shows very low E-factor (5.62 and 0.84 with and without the inclusion of water), along with multigram-scale (5.53 g) feasibility, and high regioselectivity in the case of unsymmetrical diamines and unsymmetrical α-hydroxy ketones. Furthermore, this method describes the use of a biorenewable catalyst and aqueous reaction medium for the construction of high-value heterocyclics and avoids volatile/problematic organic solvents, column-based product purifications, depleting material-based catalysts/axillaries/oxidants/purification agents/extraction agents and harsh reaction conditions. This biomimetic process can attract chemists' attention towards identifying the applicability of waste biomass-derived catalysts for the production of fine chemicals and biopotent chemical substances involving novel/interesting processes. [ABSTRACT FROM AUTHOR]

Pyrazole-assisted tetranuclear microporous polyoxovanadates(III) (POVs) (NH4)2K2[V4(μ2-OH)4(ox)4(pz)4]·9H2O (1, ox = oxalate and pz = pyrazole) and (NH4)2Na2[V4(μ2-OH)4(ox)4(4-mpz)4]·7H2O (2, 4-mpz = 4-methylpyrazole) have been constructed in reduced media, along with their triazole neutral hexa- and octanuclear products K2[V6(μ2-OH)6(ox)6(Hdatrz)6]Cl2·29.5H2O (3) and [V8(μ2-OH)8(SO3)8(Hdatrz)8]·38H2O (4, Hdatrz = 1H-1,2,4-triazole-3,5-diamine) successively. Both polyanionic structures of 1 and 2 share similar inorganic building blocks that consist of regular {V4(μ2-OH)4} skeletons with an inner diameter of 2.8 Å, while a paddle wheel-shaped cluster 3 contains a {V6(μ2-OH)6} skeleton with two chlorides encapsulated around the center of the ring, occupying a hole of 3.7 Å. An interesting isolated intrinsic polyoxometalate-based metal–organic framework (POMOF) 4 exists as an octanuclear petaloid-like skeleton {V8(μ2-OH)8(SO3)8} with an inner diameter of 5.2 Å. Bond valence sum calculations manifest that all V ions have severely reduced +3 oxidation states in 1–4, which are supported by charge balance, structural and magnetic data. Moreover, gas adsorptions indicate that 1, 2 and 4 can adsorb CO2 and O2 more favorably than N2, CH4 and H2 gases. Compared with 1 and 2, due to the functionalization of microchannels with Lewis base amino and hydroxy groups and uncoordinated azolate N-donors inside POMOF 4, it should have notable affinities toward CO2 adsorption. [ABSTRACT FROM AUTHOR]

A set of novel bis-(2-mercaptothiazoles) has been synthesized. 4,5-Difluorobenzo[1,2-d:3,4-d′]bisthiazole-2,7-dithiol (1), 4,8-difluorobenzo[1,2-d:5,4-d′]bisthiazole-2,6-dithiol (2), 4,4′,5,5′,7,7′-hexafluoro-[6,6′-bibenzo[d]thiazole]-2,2′-dithiol (3) and naphtho[1,2-d:5,6-d′]bis(thiazole)-2,7-dithiol (4) were obtained by condensation of halogenated aromatic diamines or dinitro compounds with potassium ethylxanthate or CS2 while the synthesis of benzo[1,2-d:4,5-d′]bis(thiazole)-2,6-dithiol (5) was performed starting from a centrosymmetric benzodiaminedithiol. The disodium salts of new bisthiazoles 1–5 as well as previously known benzo[1,2-d:5,4-d′]bisthiazole-2,6-dithiol (H2(dmbt)) with a formula Na2 Lx (DME)4 (L = 1–3, 5, dmbt) were synthesized from sodium sylilamide NaN(SiMe3)2 and respective bisthizoles in DME media. X-Ray srtuctural analysis revealed that the salts of bisthiazoles 2, 5 and dmbt are molecular complexes in which bisthiazoles act as ditopic ligands coordinating two sodium atoms. A similar reaction of 4 and NaN(SiMe3)2 in DME media results in a formation of 2D coordination polymer [Na2L4(DME)2]n which shows an intense photoluminescence (PL) at room temperature and 77 K. Solvent replacement in [Na2L4(DME)2]n with THF results in a formation of novel 2D coordination polymer [Na2L4(THF)4]n which turned out to be non-luminescent. Time-resolved PL spectroscopy revealed that the low temperature PL of the disodium salts consists of fluorescent and phosporescent components. Based on the phosphorescence spectra the triplet levels of the bisthizoles were found to be 21 400, 21 400, 21 500, 21 600, 18 900 and 21 200 cm−1 for bithiazoles 1–5 and dmbt respectively. [ABSTRACT FROM AUTHOR]