Search

Sulphur doped graphitic carbon nitride (SGCN) was effectively prepared and comprehensively described. A straightforward synthetic process based on thermal condensation was reported for the synthesis of SGCN using thiourea as a precursor. Cyclic voltammetry (CV) and differential pulse voltammetry were used to evaluate the electrochemical performance of cortisol. SGCN sheets were used to boost the electro-catalytic activity, exhibiting very exceptional electrochemical behaviour towards cortisol. As a result, we obtained a broad linear response range of 0.1–100 μM, as well as a comparatively low detection limit (15.8 × 10−8 M). Furthermore, the fabricated SGCN/CFP electrode shows excellent selectivity in the presence of a large number of possible interfering species. SGCN comprises (C with N and S) heteroatoms, which most likely would have led to a better current response towards cortisol detection. Furthermore, the structural defects that generate additional active sites on the surface of SGCN may enhance the quick electron transfer that occurs during the oxidation of cortisol. [ABSTRACT FROM AUTHOR]

A chromone-based symmetrical dipodal Schiff base probe L was designed and synthesized for multi-analyte detection in both aqueous and organic media. L displayed a prominent 'turn-on' fluorescence response with Al3+ (LOD = 6.9 μM) via the chelation-enhanced fluorescence (CHEF) process in a fully aqueous medium based on the inhibition of the photoinduced electron transfer (PET) process. Moreover, the in situ generated [L-Al3+] system was able to detect pyrophosphate (PPi) under identical experimental conditions. The proposed sensing pathway is believed to be the complexation with aluminium, followed by the subsequent decomplexation of the system by PPi. Furthermore, as the probe was decorated with –NH functionalities, it attained fluorescence indications upon binding with a basic anion. The detection ability of the probe for fluoride ions (LOD = 6.8 × 10−8 M) in the organic medium was studied using the 'turn-off' emission change based on the formation of a N–H⋯F hydrogen bond and subsequent deprotonation, as well as a visual change in color from yellow to reddish-yellow under UV light. The in situ prepared [L-F−] adducts could potentially sense Zn2+ ions with a 'turn-on' response via the metal-induced release of the free probe. All of the spectroscopic analyses were recorded to support the recognition mechanism of the aforementioned analytes by the reported probe molecule L. The probe also found applications in testing real water samples. [ABSTRACT FROM AUTHOR]

In this work, we developed pillar[5]arene-functionalized paper as a fluorescent sensor for cyanide ions in water. The pillar[5]arene bearing a mono-amine substituent was anchored covalently on paper by the sequence (i) oxidization of hydroxyl groups of glucoses in the cellulose, (ii) condensation with the amino group in the pillar[5]arene and (iii) reduction of the Schiff base obtained. Next, 10-methylacridinium iodide as a fluorescent indicator was introduced onto the paper by non-covalent interactions. Using a simple ultraviolet lamp, this functionalized paper could detect cyanide ions of concentration ranging from 10−7 to 10−3 M by the naked eye. [ABSTRACT FROM AUTHOR]

The New Journal of Chemistry, published by The Royal Society of Chemistry, has released its latest issue containing a variety of articles and papers on chemistry-related topics. The journal aims to connect the world with the chemical sciences and features papers on bioethanol fermentation, hydrogels in energy storage and biomedical technologies, environmentally responsible production, and other subjects. The document is a list of papers published in the journal, covering topics such as metal-organic frameworks, cycloaddition reactions, photochromic films, supercapacitors, computational predictions, catalysis, nanospheres, electrochemical sensors, and quantum dots. These papers offer valuable insights and advancements in the fields of chemistry and materials science. [Extracted from the article]

The document is a contents list for the New Journal of Chemistry, a publication that aims to connect the world with the chemical sciences. It provides information about the articles and papers included in the journal's latest issue. The articles cover a range of topics in chemistry, including the structural basis for Cu(II) metallocycle hexamer formation, photocatalyst-free hydrothiolation of gem-difluoroalkenes with thiols, and the construction of an alkynyl-containing porous polymer for enhanced photocatalytic H2O2 generation. The journal also invests its profits back into the chemistry community. Additionally, the document includes a correction to a previous paper on the effect of electrolyte optimization. [Extracted from the article]

This document is a contents list for the New Journal of Chemistry, a publication by The Royal Society of Chemistry. It includes articles covering various topics in chemistry, such as surface modulation of MXenes, synthesis of compounds, and studies on materials and their properties. The journal aims to connect the world with the chemical sciences. The listed papers in this document discuss the electrical and dielectric properties of Na2/3Mn2/3Fe1/3O2 as a cathode material for sodium-ion batteries, a fluorescent probe for monitoring lipid droplets, the effect of cis/trans isomerization on photochromic properties, and the bioactivity of benzophenazine enaminone derivatives as inhibitors of ERK2. [Extracted from the article]

The document is a contents list for the New Journal of Chemistry, a journal that focuses on new directions in chemistry. It includes a list of communications and papers featured in the journal, covering a range of topics such as catalysis, synthesis, and electrochemistry. The journal is published by The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. The document also mentions approved training courses offered by the Royal Society of Chemistry for professional development. The given document is a list of papers published in the New Journal of Chemistry in 2024. The papers cover a range of topics including DNA silver nanoclusters, graphene oxide synthesis, CO release from plasmonic Pt, and the construction of metal-organic frameworks. Other topics include the synthesis of magnetic porous organic polymers, coordination polymers, and hybrid gels. The document also includes a correction to a previously published paper. [Extracted from the article]

The article focuses on recent advancements in chemistry, highlighting the development of new materials and chemical processes. Topics include the synthesis of insensitive energetic materials with enhanced detonation performance, the use of vanadium(V) complexes for syndiospecific ring-opening metathesis polymerization (ROMP) of cyclic olefins, and the exploration of metal-support interactions to enhance catalytic activity for hydrogen production.

O-Vanillin derived Schiff base 1-[(E)-(2-hydroxy-3-methoxybenzylidene) amino]-4-methylthiosemicarbazone (VCOH) has been synthesized for colorimetric and fluorescence chemosensors towards PO43− ions. A fluorescence 'turn-on' sensing mechanism of VCOH towards PO43− ions has been explained due to emission from the VCO− ion formed upon transfer of the phenolic proton of VCOH to a PO43− ion. The 1 : 1 stoichiometry between the VCOH probe and PO43− ion is confirmed by Job's plot based on UV-vis titration. The limit of detection (LOD) of VCOH towards PO43− ions is found to be 0.49 nM. The PO43− ion sensing property of probe VCOH has been applied to prepare portable paper strips and for the analysis of real water samples. Fluorescence 'turn-on' and 'turn-off' responses of VCOH towards PO43−and H+ respectively have been used to construct a molecular logic gate. Fluorescence based sensing studies in which the concentration of analytes is adjusted over a broad range can be both laborious and expensive. In order to address these challenges, we have utilized various soft computing methods, including artificial neural networks (ANN), fuzzy logic (FL), and adaptive neuro-fuzzy inference systems (ANFIS), to appropriately model the 'turn-on' and 'turn-off' behaviors of the VCOH probe upon addition of PO43− and H+ respectively as well as to predict the experimental sensing data. [ABSTRACT FROM AUTHOR]

The New Journal of Chemistry is a publication that features research papers on various topics in chemistry. The current issue includes articles on the synthesis of compounds, the development of catalysts, and the investigation of chemical reactions. Each paper presents its own findings and conclusions based on the research conducted. The document also provides information for authors on how to submit their own material for publication. [Extracted from the article]

The New Journal of Chemistry is a publication that features research papers on various topics related to chemistry. It is a collaboration between The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. The current issue includes articles on the stabilization of emulsion gels, antioxidant activity of lignans, electrostatic potential in hydrogen bond formation, and the synthesis of compounds for different applications. Each paper provides detailed information on the research conducted and the findings obtained. The document also provides information for authors on how to submit their own research for publication. [Extracted from the article]

Two Schiff bases based on triphenylamine and phenothiazine, namely DTPA-SB and DPTZ-SB, respectively, were synthesized via facile organic transformations. The mixing of these two molecules with rhodamine B dye (Rh-B) resulted in efficient white light generation in the solution state as well as in the ionic liquid medium of [Bmim][Cl] with the Commission Internationale de l'Eclairage (CIE) coordinates of (0.33, 0.35) and (0.34, 0.35), respectively. Notably, the generation of white light in the ionic liquid medium has been reported for the first time. Several mechanistic studies, namely fluorescence titration, spectral overlap, Förster distance calculation and DFT studies, established that the mechanism of WLE is Förster resonance energy transfer with simultaneous emission. On a parallel note, DTPA-SB showed an excellent fluorescence sensing response towards 30% H2O2 with a remarkable limit of detection (LOD) of 8.4 × 10−7 M, while DPTZ-SB exhibited a slight decrease in the emission intensity with a LOD of 1.96 × 10−7 M. Both DTPA-SB and DPTZ-SB were specifically selective for 30% H2O2 without interference from fifteen other chemical species. Since DTPA-SB exhibited significant response towards hydrogen peroxide detection, a paper-based fluorescent sensor device was fabricated by embedding DTPA-SB on the filter paper with a LOD of 2.3 × 10−9 M. Additionally, a smartphone color-scanning app was tuned with the paper-based sensors to perform scanometric tests. A paper-based device for hydrogen peroxide sensing by applying a simple fluorescent Schiff base is reported herein for the first time. [ABSTRACT FROM AUTHOR]

The New Journal of Chemistry, published by The Royal Society of Chemistry, has released its latest issue which includes a variety of articles covering different topics in the field of chemistry. The papers discuss recent progress in areas such as nitrogen-heterocycles, chemisorption of gases, photoactive derivatives, and potential applications of nanoribbons. The journal aims to connect the global community with the chemical sciences and provides scientific insights and advancements in various fields of study. [Extracted from the article]

The synthesis and full characterization using various spectroscopic techniques and single-crystal X-ray diffraction analysis of a family of three robust copper(ii)-centered complexes with organometallic donor–acceptor substituted unsymmetrical Schiff base ligands, namely, the binuclear derivatives Cu[Fc–C(O)CHC(CH3)N–X–NCH-(2-O,5-Br–C6H3)] (3: X = o-C6H4, 4: X = CH2CH2), and the corresponding ionic trinuclear counterpart of 4, [Cu{Fc–C(O)CHC(CH3)N–CH2CH2–NCH-(η6-2-O,5-Br–C6H3)RuCp*}][PF6] (5) (Fc = (η5-C5H5)Fe(η5-C5H4), Cp* = η5-C5Me5), have been explored. Single crystal X-ray diffraction analysis of complex 3indicates a bowed structure of the unsymmetrical Schiff base scaffold. The Cu2+ion is tetracoordinated in a square planar environment, with two nitrogen atoms and two oxygen atoms as donors. The EPR spectra of solid trinuclear complexes 5and 7(unsubstituted salicylidene ring and X = o-C6H4) at low temperature (68 K) consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) values of 0.0458 and 0.0415 cm−1, respectively, and a half-field signal (ΔMs = ±2) at ca.1600 G, suggesting the formation of dimeric species (S= 1). In those dimers, Cu–Cu distances of 3.97 and 4.14 Å, respectively, are computed from ZFS terms. The variable-temperature (2–300 K) magnetic susceptibilities of powdered samples of 5and 7have been measured, and an intermolecular antiferromagnetic interaction with exchange couplings of J= −1.05 and −0.65 cm−1, respectively, were found. The electrochemical behavior of both the neutral binuclear and ionic trinuclear compounds was investigated by cyclic voltammetry. Notably, the ability of the copper Schiff base core to transmit electronic effects between the two organometallic termini has been demonstrated by the observed anodic shift of the reversible voltammetric signal ascribed to the FeII/FeIIIcouple of the ferrocenyl donor fragment. [ABSTRACT FROM AUTHOR]

We describe a simple method for the covalent immobilisation of proteins to hydrogen-terminated silicon surfaces and demonstrate various protein detection strategies. Using hydrosilation chemistry, 1-undecenylaldehyde is attached to the surface through stable Si–C bonds; the reaction occurs primarily viathe vinyl group and mainly aldehyde groups are presented at the top surface of the monolayer. Proteins are then captured by reaction with their surface lysines. The proteins are bound viaa Schiff base, whose formation is reversible, but can be fixed by reduction with cyanoborohydride in a one-pot reaction. Using standard methods of patterning, we were able to specifically localise proteins (urease, amyloid beta (Aβ1–42), GFP and TolAIII-GFP) with little non-specific adsorption at non-reactive sites. We characterised the immobilised proteins by X-ray photoemission spectroscopy, atomic force microscopy and FTIR, and showed that they retain their functionality using potentiometry, fluorescence and coupled antibody systems with chromogenic substrates. We also exploited the conductivity of the silicon substrate to demonstrate electrochemical detection of surface-bound proteins. These protocols will aid the development of protein biochips based on silicon, which gives rise to the possibility of detecting protein–protein and protein–small molecule interactions electronically. Such chips would be expected to be of utility for comparative proteomics and in molecular medicine, drug discovery and diagnostics. [ABSTRACT FROM AUTHOR]

In this paper, we present the synthesis of four new complexes: the dimeric precursor [Ir(dmppz)2(μ-Cl)]2 (1) (Hdmppz -- 3,5-dimethyl-1-phenyl-1H-pyrazole) and heteroleptic bis-cyclometalated complexes: [Ir(dmppz)2(Py2CO)]PF6•½CH2Cl2 (2), [Ir(dmppz)2(H2biim)]PF6•H2O (3), and [Ir(dmppz)2(PyBIm)]PF6 (4), with auxiliary N,N-donor ligands: 2-di(pyridyl)ketone (Py2CO), 2,2'-biimidazole (H2biim) and 2-(2'-pyridyl)benzimidazole (PyBIm). In the obtained complexes, SC-X-ray analysis revealed that Ir(III) has an octahedral coordination sphere with chromophores of the type {IrN2C2Cl2} (1) or {IrN4C2} (2-4). The complexes obtained, which have been fully characterised by physicochemical methods (CHN, TG, FTIR, UV-Vis, PL and ¹H, 13C, 15N NMR), were used to continue our studies on the factors influencing the cytotoxic properties of potential chemotherapeutic agents (in vitro). To this end, the following studies are presented: (i) comparative analysis of the effects on the biological properties of N,N-donor ligands and C,N-donor ligands in the studied complexes, (ii) studies of the interactions of the compounds with the selected molecular target: DNA and BSA (UV-Vis, CD and PL methods), (iii) and the reactivity towards redox molecules: GSH, NADH (UV-Vis and/or ESI-MS methods), (iv) cytotoxic activity (IC50) of potential chemotherapeutics against MCF-7, K-562 and CCRF-CEM cell lines. [ABSTRACT FROM AUTHOR]

In this paper, three different Zn(II) complexes with (E)-2-(2-(1-(6-bromopyridin-2-yl)ethylidene)hydrazinyl)-N,N,N-trimethyl-2-oxoethan-1-aminium chloride (HLCl) have been synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR and NMR spectroscopy. All complexes are mononuclear, with the ligand (L) coordinated in a deprotonated formally neutral zwitterionic form via NNO donor set atoms. Complex 1 forms an octahedral geometry with the composition [ZnL2](BF4)2, while complexes 2 [ZnL(NCO)2] and 3 [ZnL(N3)2] form penta-coordinated geometry. Density functional theory (DFT) calculations were performed to enhance our understanding of the structures of the synthesized complexes and the cytotoxic activity of the complexes was tested against five human cancer cell lines (HeLa, A549, MDA-MB-231, K562, LS 174T) and normal human fibroblasts MRC-5. Additionally, antibacterial and antifungal activity of these complexes was tested against a panel of Gram-negative and Gram-positive bacteria, two fungal strains, and a yeast strain. It is noteworthy that all three complexes show selective antifungal activity comparable to that of amphotericin B. Molecular docking analysis predicted that geranylgeranyl pyrophosphate synthase, an enzyme essential for sterol biosynthesis, is the most likely target for inhibition by the tested complexes. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. The contents list includes various papers on topics such as acoustic shockwave-induced morphological transformation, copper-organic frameworks, and the assembly of poly(3-hydroxybutyrate). The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document also mentions other journals in the field of environmental science. [Extracted from the article]

A novel fluorescent material that can change its emission properties in response to different external stimuli holds significant importance for the development of sensors, information storage, and encryption materials. In this work, we designed and synthesized two zinc(II) coordination compounds, [Zn(HL)I2]·CH3OH (1) and [Zn(HL)Br2]·CH3OH (2), which exhibit remarkable changes in their emission properties under three different external stimuli. The two compounds were prepared using a simple one-pot method by reacting zinc(II) salts with 4-(N,N-diphenylamino)benzaldehyde and 3-amino-2-pyridinone. Under the stimulation of NH3 vapor, both compounds underwent decomposition, leading to a transformation of their fluorescence from yellow to blue, exhibiting a significant blue-shift of more than 170 nm. After exposure to HCl vapor, the fluorescence color of the two original compounds changed from yellow to red, and the color change could be easily distinguished by the naked eye under UV light irradiation. Then after fumigation with NH3 vapor, the color of both samples changed from red to blue. Based on the high-contrast NH3-responsive properties and HCl-responsive properties, we designed and developed test papers capable of detecting HCl vapor and NH3 vapor. Furthermore, due to the transformation from the crystalline state to the amorphous state during grinding, the two compounds also demonstrated high-contrast mechanochromic luminescence properties. After grinding, the color of the two compounds changes significantly from yellow to orange. [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]

In this paper, we report the synthesis and characterization of a mononuclear zinc complex (1) containing a redox-active bis(4-antipyrinyl) derivative of the 3-cyanoformazanate ligand. Complex 1 was readily obtained by refluxing zinc acetate with 3-cyano-1,5-(4-antipyrinyl)formazan (LH) in a methanolic solution. Single-crystal X-ray diffraction analysis of complex 1 shows that the formazanate ligands bind to the zinc center in a five-member chelate "open" form via the 1- and 4-positions of the 1,2,4,5-tetraazapentadienyl formazanate backbone leading to the formation of the mononuclear bis(formazanate) zinc complex exhibiting a distorted octahedral geometry. We also report the study of resistive-switching random access memory application of this solution-processable bis(formazanate) Zn(II) complex to facilitate the practical implementation of transition metal complex-based molecular memory devices. The complex demonstrated high conductance switching with a large ON–OFF ratio, good stability, and a long retention time. A trap-controlled space charge limited current mechanism is proposed for the observed resistive switching behavior of the device, wherein the role played by the [ZnIIL2] complex that comprises the extended redox-active conjugated ligand backbone is revealed by corroborating electrochemical studies, spectrochemical experiments, and DFT calculations. In addition to providing significant insights into the molecular design of transition metal complexes for memory applications, this study also presents the utilization of ZnIIL2 towards the realization of non-volatile resistive random access memory (RRAM) devices with inorganic/organic hybrid active layers that are highly cost-effective and sustainable. These devices exhibited multilevel switching and low current operation, both of which are desirable for advanced memory applications. [ABSTRACT FROM AUTHOR]

In this paper, we use mono- and bimetallic complexes based on Earth-abundant, cheap and benign zinc for the synthesis of sustainable aliphatic and semi-aromatic polyesters. Tridentate and hexadentate aldimine-thioetherphenolate ligands were used to obtain the desired zinc complexes by the reaction of proligands with opportune equivalents of zinc bis[bis(trimethylsilyl)amide]. The obtained bimetallic complexes 1 and 2 and the monometallic complex 3 were used as catalysts in the Ring-Opening Polymerization (ROP) of landmark cyclic esters, such as ε-caprolactone and lactide, and in the Ring-Opening COPolymerization (ROCOP) of cyclohexene oxide and phthalic anhydride under different reaction conditions. All catalysts were active in these two classes of reactions, showing good control of the polymerization processes. Interestingly, the bimetallic complexes have higher activity compared to their monometallic counterparts, highlighting the cooperation between the two zinc centers. [ABSTRACT FROM AUTHOR]

In this article, a novel triphenylamine-modified salicylaldehyde Schiff base 2-(((4-(diphenylamino)phenyl)imino)methyl)-4-(pyridine-4-yl)phenol (HL) was synthesized and structurally characterized. HL possessed D–π-A structure and exhibited typical AIE property in THF/H2O. It was applied to selectively recognize Cu2+ through an on–off mode in THF/H2O (1/9, v/v), and the fluorescence attenuation was attributed to a paramagnetic quenching effect of Cu2+ together with the abatement of HL aggregates. Hence, the detection limit achieved was as low as 1.32 × 10−7 M. The spectroscopic and ESI-HRMS results revealed a 1 : 2 complexation ratio of Cu2+ with HL. The mechanism for sensing Cu2+ was further confirmed by performing DFT calculations. Owing to the large affinity between Cu2+ and His, the resultant CuL2 system was further used to detect His via the off–on method based on the displacement of ligands. The detection limit for His reached 5.14 × 10−8 M. Furthermore, HL was available to prepare handy indicator papers for the on-site recognition of Cu2+ and His. Confocal fluorescent imaging demonstrated that HL could sequentially respond to intracellular Cu2+ and His. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. The issue includes articles on topics such as protein crystallization techniques, crystal structure analysis, construction and catalytic effects of solvent-dependent products, and the discovery of new solid forms of dipeptide. The journal is published by The Royal Society of Chemistry, a leading chemistry community that invests its profits back into the chemistry community. [Extracted from the article]

An acetonitrile solvate of a Schiff base molecule (HL) with acetonitrile (HL·2CH3CN) and its Cd(II) complex (Cd(HL)2Cl2, 1) was designed and synthesized. The different conformation of HL in HL·2CH3CN is adjusted by the hydrogen bonding O–H⋯O between HL molecules, together with N–H⋯N between HL molecules and acetonitrile molecules. Meanwhile, the conformation of HL in complex 1 is adjusted by coordination interactions between Zn ions and atoms O and N, together with hydrogen bonding N–H⋯Cl. The presence of the triphenylamine group makes HL·2CH3CN and complex 1 loosely packed. Upon grinding, HL·2CH3CN and complex 1 both showed high-contrast mechanochromic luminescence (MCL) change from blue to green and cyan to yellow, respectively. These changes can be eliminated by fumigation with organic vapor. The results of powder X-ray diffraction (PXRD) show that their MCL is due to the phase transformation from a crystalline state to an amorphous state. In addition, HL·2CH3CN and complex 1 also exhibited high-contrast acidochromism upon exposure to HCl and NH3 vapor. X-ray photoelectron spectroscopy (XPS) and PXRD studies show that the protonation of the –NH– group together with phase transformation from a crystalline state to an amorphous state is attributed to the fluorescence switching. For HL·2CH3CN, the protonation process was accompanied by the departure of acetonitrile molecules. The emission of HL was restored to the amorphous state rather than the original crystalline state emission after further exposure to NH3 vapor, while 1-HCl could revert to the original crystalline state emission. In addition, HL·2CH3CN and complex 1 have been successfully used to produce writable and acid-responsive test papers. [ABSTRACT FROM AUTHOR]

Excited state intramolecular proton transfer (ESIPT) process-based organic fluorophores provide an opportunity to develop large Stokes-shifted multifunctional fluorescence systems for light emitting, chemosensing and bioimaging applications. In this manuscript, ESIPT molecules with two thiazole ring fused symmetrical (1) structures and one thiazole and a Schiff base functional unsymmetrical (2) structure were synthesized, and the impact of their extended π-conjugation was investigated on the fluorescence properties in the solid and solution state as well as metal ions sensing. The strong intramolecular H-bonding and multiple intermolecular H-bonds in the crystal lattice of 1 and 2 lead to ESIPT-induced solid state fluorescence (λmax = 549 (1) and 580 nm (2); ΦF = 7.6 (1) and 6.1% (2)). Interestingly, the molecular assembly of 2 in the solid state facilitated mechanical stimuli-induced reversible fluorescence switching, whereas the flat molecular arrangement in 1 did not show recovery of fluorescence. In contrast, 1 showed strong fluorescence in solution (ΦF = 0.59 in DMF compared to quinine sulphate) due to its symmetrical structure, with strong intramolecular H-bonding, but the PET effect contributed to the very weak fluorescence of 2. The strong solution and solid state fluorescence coupled with the metal chelating functionality of 1 and 2 showed highly selective fluorescence sensing of Cu2+ ions in aqueous solution. 1 and 2 revealed detection limits of 130 and 10 nM, respectively, for Cu2+ ions, which are significantly lower compared to the WHO-recommended level (1.3 mg L−1). The strong solid state fluorescence of 1 and 2 was further used for fabricating filter paper-based fluorescence sensors for the selective sensing of Cu2+ ions. [ABSTRACT FROM AUTHOR]

Three bis-benzimidazolyl bidentate ligands with phenolyl ether linkers, 1,n-bis[2-(1H-1,3-benzimidazol-1-ylmethyl)phenoxy]alkane (L1: n = 1, L2: n = 3, L3: n = 4), and their six metal complexes were synthesized by the reactions of the respective ligands with metal salts. The six metal complexes included two cobalt(II) complexes ([Co(L1)(NO3)2] (1) and [Co(L3)(LA)]n (6) (LA = maleate)), two copper(II) complexes ([Cu(L1)(SO4)]2 (4) and [Cu(L3)(SO4)]2 (5)), one zinc(II) complex ([Zn(L1)(NO3)2] (2)) and one nickel(II) complex ([Ni(L2)(NO3)2] (3)). Complexes 1 and 2 had one 16-membered macrometallocycle, and complex 3 had one 18-membered macrometallocycle. In complexes 4 and 5, two SO42- joined two macrometallocycles together (16-membered macrometallocycle for 4 and 19-membered macrometallocycle for 5). In complexes 1-5, each macrometallocycle was constructed from one ligand and one metal ion. In complex 6, 19-membered macrometallocycles were connected together by maleate groups (LA) to form a 1D polymeric chain, where each 19-membered macrometallocycle was constructed from one L3 and one Co(II) ion. In crystal packings of complexes 1-6, H-bonds, π--π interactions and C--H•••π contacts participated in the formation of 2D supramolecular layers and 3D supramolecular architectures. The conformations of complexes 1-6 were also analyzed. Additionally, the recognition performance of complex 1 as a chemosensor for HSO4- was studied through fluorescence spectra, UV/vis spectra, 1H NMR titrations, HRMS spectra and IR spectra. The large binding constant (1.81 x 104 M-1) showed that there was a strong acting force between 1 and HSO4-, and the low detection limit (1.40 x 10-7 mol L-1) indicated that the detection of 1 for HSO4- was sensitive. The experimental results showed that complex 1 can effectively differentiate HSO4- from other anions. [ABSTRACT FROM AUTHOR]

The reaction of Schiff base ligand N,N′-bis(salicylidene)ethylenediamine (H2L) with [CoII2(μ-OH2)(O2CCMe3)4(HO2CCMe3)4] (CoII2-Piv) (Piv = pivalate) and Ln(NO3)3·xH2O (for 1, 3, 4x = 5; for 2, x = 6) salts in the presence of triethylamine afforded [CoIIILnIII(L)(μ-Piv)2(η1-Piv)2(η1-OHMe)2] [where Ln = Dy, for 1; Tb, for 2; Ho, for 3; and Er, for 4] complexes. The heterometallic dinuclear ensemble is built via the bridging coordination action of [L]2− and four [Piv]− ligands. Further, the Ln(III) center is coordinated by two η1-OHMe ligands. Shape analysis of all the Ln(III) centers in 1–4 reveals the existence of a distorted triangular dodecahedron geometry. Magnetic studies revealed that compound 1 shows slow magnetic relaxation under zero-field at low temperatures whereas compound 4 displays field-induced slow magnetic relaxation. This phenomenon is in agreement with the results of theoretical studies. [ABSTRACT FROM AUTHOR]

The equimolar reaction between 1,9-bis(N,N-dimethylaminomethyl)-5,5′-diphenyldipyrromethane, H2L1 or 1,9-bis(3,5-dimethylpyrazolylmethyl)-5,5′-diethyldipyrromethane, H2L2 and [NiCl2(DME)] in the presence of KH yielded the neutral mononuclear nickel(II) complexes [Ni(L1)-κ4N,N,N,N], 1 and [Ni(L2)-κ4N,N,N,N], 2, respectively. Their X-ray structures revealed the formation of triple chelation by the ligand in both structures with quite different nickel(II)-surrounded square planar geometries owing to the steric difference between –NMe2 and 3,5-dimethylpyrazolyl groups. While the –NMe2 group substituted ligand L1 afforded nickel complex 1 with a plane of symmetry, 3,5-dimethylpyrazole substituted L2 rendered helical chirality in the structure of complex 2. Both the enantiomers (Δ and Λ) of complex 2 were observed in the crystal lattice. Their solution state behaviors were consistent with the solid-state structures as monitored by 1H NMR spectroscopy. Both the enantiomers of complex 2 were present in a dynamic equilibrium in solution and studied by variable temperature 1H NMR spectroscopy. Similar to the chiral complex, the corresponding ligand H2L2 also exhibited chirality as shown by its crystal structure and the two ligand enantiomers participated in a very fast dynamic interconversion, which became slower upon metalation. [ABSTRACT FROM AUTHOR]

Two mononuclear complexes, [Cu(L1)2] (complex 1) and [Cu(HL2)2](NO3)2 (complex 2) where HL1 is 1-((cyclohexylmethylimino)methyl)-naphthalen-2-ol and HL2 is 4-bromo-2-((2-morpholinoethylimino)methyl)phenol, have been synthesized under mild conditions and characterized by different standard analytical methods. Single crystal X-ray diffraction analysis shows that the copper atoms in both copper(II) complexes are in a square planar geometry. These complexes have been used as catalysts in the oxidation of benzyl alcohol and benzyl alcohol with various substituents in the presence of NaOCl as the terminal oxidant. The results show that complex 1 acts as a better catalyst than the other with the highest yield of 91% in the case of 4-methoxy benzyl alcohol oxidation. The copper complex transfers the oxygen of sodium hypochlorite to the alcohol to produce the aldehyde. The use of NaOCl as an oxidant in alcohol oxidation is rare although it is cheap and nonexplosive. [ABSTRACT FROM AUTHOR]

Square planar complexes of Ni(II) and Pd(II) of a new redox-active pentadentate azo-appended 2-aminophenol ligand (H4L = N,N′-bis(2-hydroxy-3,5-di-tert-butylphenyl)-2,2′-diamino-ortho-azobenzene) in three accessible redox levels [amidophenolate(2−), semiquinonate(1−) π radical, and quinone(0)] were synthesized. The coordinated HL(3−) ligand provides four donor sites [two N(iminophenolates), an N′(azo), and an O(phenolate)], while the phenolic OH group remains free in the three complexes. Cyclic voltammetry on complex [Ni(L)] 1 and its corresponding Pd(II) analogue [Pd(L)] 2 in CH2Cl2 displayed three redox responses (two oxidative at E1/2 = 0.06 V and Epa (anodic peak potential) = 0.80 V and one reductive at −0.77 V for 1 and at E1/2 = 0.08 V and Epa = 0.85 V and at −0.74 V for 2vs. Fc+/Fc). The chemical oxidation of 1 with AgSbF6 afforded [Ni(L)]SbF6·2CH2Cl2 (3·2CH2Cl2). Complex [Pd(L*)] 4, which is coordinated by a phenoxazinyl derivative of L(4−), was obtained via intraligand cyclization in the parent complex 2 under basic oxidizing conditions. The molecular structures of 1, 2, 3·2CH2Cl2 and 4 were elucidated through X-ray crystallography at 100 K. Characterization using 1H NMR, X-band EPR, and UV–VIS–NIR spectroscopy established that the complexes have [NiII{(LISQ)˙2−}] 1, [PdII{(LISQ)˙2−}] 2, [NiII{(LIBQ)−}]SbF6/1+SbF6−(3), and [PdII{(L*AP)˙2−}] 4 electronic states. Complexes 1, 2, and 4 possess paramagnetic St (total spin) = 1/2 ground-state, whereas 3 is diamagnetic (St = 0). Density functional theory (DFT) electronic structural calculations at the B3LYP level rationalized the observed experimental results. Time-dependent (TD)-DFT calculations allowed us to identify the nature of the observed absorption spectra. [ABSTRACT FROM AUTHOR]

We present herein magneto-structural studies of three heterometallic Zn2Dy complexes: [Zn2Dy(L)2Cl2(H2O)](ClO4)·4H2O (1), [Zn2Dy(L)2Br2(H2O)](ClO4)·4H2O (2) and [Zn2Dy(L)2(OAc)I(H2O)]I3·4H2O (3), utilizing a new Schiff base ligand, N,N'-bis(3-methoxy-5-methylsalicylidene)-1,2-diaminocyclohexane (H2L). Complexes 1 and 2 exhibit remarkable magnetic relaxation behaviour with relatively high energy barriers in zero field (Ueff: 244 K for 1 and 211 K for 2) and notable hysteresis temperatures, despite the low local geometric symmetry around the central DyIII ions. The SMM performance of these complexes is further enhanced under an applied magnetic field, with Ueff increasing to 309 K for 1 and 269 K for 2, positioning them as elite members within the Zn–Dy SMM family. These findings emphasize the substantial influence of remote modulation on ZnII beyond the first coordination sphere of DyIII ions on their dynamic magnetic relaxation properties. Ab initio studies demonstrate that the relative orientation of the phenoxo-oxygen donor atoms around the DyIII ion is critical for determining the magnetic anisotropy and relaxation dynamics in these systems. Additionally, experimental and theoretical investigations reveal that the coordination of the bridging acetate towards the hard plane, combined with significant distortion from the ideal ZnO2Dy diamond core arrangement caused by the acetate ion, results in low magnetic anisotropy in complex 3, thereby leading to field-induced SMM behaviour. Overall, this study unveils the effects of co-ligands on the SMM performance in a series of linear trinuclear Zn–Dy–Zn complexes, which exhibit low local geometric symmetry around the DyIII centres. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) constitute an assorted class of multi-dimensional materials that offer the potential to serve as luminescent sensors for the sensitive and selective detection of antibiotics in wastewater. Herein, a new Zn(II)-based MOF with the formula [Zn(PMA)0.5(bbp)·H2O·DMA] (1) (bbp = 3,5-bis(benzoimidazo-1-ly)pyridine; PMA = pyromellitic acid) was synthesized by a solvothermal method and characterized. Crystallographic analysis reveals that MOF 1 possesses a 4,4-connected net with the Schläfli symbol {32·4·52·6}2{32·42·52}. The fabricated MOF exhibited luminescent property and was employed as a luminescent sensor to sensitively and selectively detect tetracycline (TCY) antibiotic amongst thiamphenicol (THI), 2-methyl-4-chlorophenoxyacetic acid (MCPA), tetracycline (TCY), sulfamethoxazole (SMT), thiabendazole (TBZ), tinidazole (TDZ), sulfadiazine (SDZ), chloramphenicol (CAP), metamitron (MMT), and dinotefuran (DTF). Further, restoration of the emissive response of TCY@1 was achieved by adding salicylic acid with a concomitant bathochromic shift in the emissive response. The possible sensing mechanism and restoration of emissive response were assessed with the aid of theoretical calculations. [ABSTRACT FROM AUTHOR]

Eugenol, the major constituent of clove oil, has been explored as an essential natural ingredient for ages owing to its versatile pharmacological properties. However, to date, the coordination chemistry of eugenol derivatives has not been much explored. In the present work, an eugenol-based Schiff base ligand (HL) was synthesized and structurally confirmed through ESI-MS, NMR, and FT-IR spectroscopy studies. Consequently, the N,O-donor chelating ligand HL was coordinated with Cd2+, in the presence of bridging pseudohalides (thiocyanate, SCN−, and dicyanamide, N(CN)2−) to synthesize two luminescent coordination polymers (CPs 1 and 2): [Cd2(L)2(X)2]n (where HL = 4-allyl-2-(((2-(benzylamino)ethyl) imino)methyl)-6-methoxyphenol and Xs are bridging pseudohalides, i.e., SCN− and N(CN)2−) on a Cd-eugenol scaffold. The CPs depicted structural diversity, bulk-phase purity, thermal stability, and the presence of interlayer supramolecular C–H⋯π interactions together with C–H⋯S (for CP 1) and C–H⋯N (for CP 2) interactions. The CPs further exemplified themselves as selective and sensitive 'turn-off' probes towards trinitrophenol (TNP) (quenching efficiency: 82.02% and 83.86% for 1 and 2) among a pool of hazardous nitroaromatic compounds (NACs). Accordingly, 1 and 2 exhibited an ultralow limit of detection (LOD) of 0.29 and 0.15 μM, with high quenching constants (KSV) of 5.91 × 104 and 17.60 × 104 M−1, respectively. In addition, TNP sensing events were evidenced to be recyclable and exhibited fast response (∼31 s, 1, and ∼40 s, 2), which increased its real-world viability. Vapor phase TNP sensing was also accomplished upon drop-casted CP films. Experimental investigations and theoretical DFT study confirmed the cooperative occurrence of RET-IFE-PET-collisional quenching and non-covalent π⋯π stacking as key factors involved in the TNP sensing performance. The competency of 1 and 2 in the detection of TNP from several complex environmental matrices (CEMs), viz. matchstick powder, river and sewage water, and soil specimens, was also established with good recovery (∼66–86% and ∼68–93% for 1 and 2, respectively) and high KSV values (3.90–11.39 × 104 and 6.17–18.79 × 104 M−1 for 1 and 2, respectively). [ABSTRACT FROM AUTHOR]

We synthesized a sublimable molecular spin crossover Fe(II) complex based on the Schiff base tridentate ligand qsal-NEt2 (5-diethylamino-2-((quinolin-8-ylimino)methyl)phenol). The compound undergoes a transition in temperature with thermally induced excited spin state-trapping (TIESST) for high-temperature sweep rates, which can be suppressed by reducing the sweep rate. The X-ray absorption spectroscopy (XAS) studies on the microcrystalline powder confirm the TIESST effect. The molecules are deposited under ultra-high vacuum on a graphene/SiO2 substrate as a submonolayer. Investigation of the submonolayer by XAS reveals the molecular integrity and shows a spin crossover for the whole temperature range from 350 to 4 K, with residual HS species at low temperature and no TIESST effect. DFT calculations suggest a distribution of energetically similar adsorption configurations on graphene, i.e., with smooth crossover behaviour and the absence of TIESST, consistent with very weak intermolecular interactions and the absence of large molecular islands within the submonolayer. [ABSTRACT FROM AUTHOR]

The synthesis of eleven new nickel Schiff base complexes each bearing four pendant groups is reported. The structures of the complexes differ in the identity of the pendant groups and/or diamine moiety. All complexes were characterised by microanalysis, Nuclear Magnetic Resonance (NMR) spectroscopy and Electrospray Ionisation Mass Spectrometry (ESI-MS), while the solid-state structures of two of the molecules were also determined using X-ray crystallographic methods. The DNA binding properties of the nickel complexes with double stranded DNA and a range of G-quadruplex DNA structures was explored using different spectroscopic methods as well as computational techniques. Results from ESI-MS experiments and Fluorescent Indicator Displacement (FID) assays were consistent with each other and indicated that varying the diamine moiety had less influence on DNA affinity than changing the pendant groups. These conclusions were also generally supported by results obtained from UV melting experiments and Fluorescence Resonance Energy Transfer (FRET) assays. The cytotoxicity of selected examples of the new complexes, and close analogues reported recently, towards V79 Chinese hamster lung cancer cells and THP-1 human leukemia cells was measured. All were found to display modest cytotoxicity, with flow cytometry experiments suggesting an apoptotic pathway was the most likely mechanism of cell death. [ABSTRACT FROM AUTHOR]

Biobased hydrogels have been widely used in drug delivery, tissue engineering and biosensors due to their abundance, non-toxicity and biocompatibility. However, constructing fully biobased hydrogels with good mechanical performance still remains a challenge. Herein, a double network (DN) hydrogel consisting of oxidized hydroxypropyl guar gum (OHPG) and gelatin (Gel) was fabricated via Schiff base reaction. The Gel-OHPG hydrogel had an elongation at break of 497%, a tensile stress of 0.44 MPa and a compressive stress of 25.91 MPa. Then, the mechanical properties of the hydrogel were further enhanced through immersing it in an ammonium sulfate (AMS) solution due to the Hofmeister effect. Its elongation could reach 629% and the corresponding tensile toughness and compressive stress were 3.86 MPa and 59.55 MPa, respectively. The conductivity of the hydrogel was 0.86 S m−1. Furthermore, the Gel-OHPG hydrogel was fabricated as a flexible sensor, and it could accurately monitor human joint motions such as fingers, wrists, knees, elbows, throat and neck. Henceforth, the Gel-OHPG hydrogel prepared using fully natural polymers has promising potential in flexible sensors and tissue engineering. [ABSTRACT FROM AUTHOR]

Two halogenated Schiff bases namely, (E)-1-(((2,6-dichlorophenyl)imino)methyl)naphthalen-2-ol (L1) and (E)-1-(((4-bromo-2,6-dichlorophenyl)imino)methyl)naphthalen-2-ol (L2) were synthesized and reacted with copper(II) nitrate trihydrate in ethanol to give Cu(L1)2 (1) and Cu(L2)2 (2). All the ligands and complexes were successfully characterized using FT-IR, UV-Vis, 1H & 13C-NMR as well as mass spectra and the purity was ascertained by elemental analysis. Electron paramagnetic resonance (EPR) was used to confirm the paramagnetic nature of 1 and 2. Furthermore, the single X-ray crystal structures of 1 and 2 were determined, confirming the formation of mononuclear species in which the Cu(II) center was bonded to two bidentate Schiff bases (L1 or L2) adopting a slightly distorted square planar geometry. Density Function Theory studies revealed that, complex 2 with lowest energy band gap (ΔE) of 2.49 eV is the most reactive among the compounds. α-Amylase and α-glucosidase assays were used to evaluate the antidiabetics potential of the compounds. Complexes 1 and 2 displayed very promising antidiabetic activities with IC50 values of 148.126 mM and 107.786 mM for α-amylase assay while it was 171.559 mM for acarbose (reference drug). The antioxidant potential of the compounds was investigated using nitric oxide (NO), ferric reducing ability power (FRAP) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) assays. The compounds showed moderate to good antioxidant activities with 1 and 2 having IC50 values of 100.044 mM and 247.463 mM for NO scavenging assay, which relatively surpass Vanillin with IC50 value of 466.626 mM. All the compounds showed poor to moderate results against Escherichia coli, Staphylococcus aureus, Bacillus substilis, and Pseudomonas aeruginosa. However, none of them were active against Klebsiella pneumoniae. Generally, 1 and 2 displayed better antidiabetes, antioxidant, and antibacterial potential than L1 and L2. Predicted physicochemical and pharmacokinetic properties of all the compounds showed minimal violation of Lipinski's Ro5. [ABSTRACT FROM AUTHOR]

Treatment of [Co(N2)(tBuPNP)] (tBuPNP = anion of 2,5-bis(di-tert-butylphosphinomethyl)pyrrole) with one equivalent of an aryl azide generates the four-coordinate imido complexes [Co(NAr)(tBuPNP)] (Ar = mesityl, phenyl, or 4-tBu-phenyl). X-ray crystallographic analysis of the compounds shows an unusual square-planar geometry about cobalt with nearly linear imido units. In the presence of the hydrogen atom donor, TEMPOH, [Co(NPh)(tBuPNP)] undergoes addition of the H atom to the imido nitrogen to generate the corresponding amido complex, [Co(NHPh)(tBuPNP)], whose structure and composition were verified by independent synthesis. Despite the observation of H atom transfer reactivity with TEMPOH, the imido complexes do not show catalytic activity for C–H amination or aziridination for several substrates examined. In the case of [Co(NPh)(tBuPNP)], addition of excess azide produced the tetrazido complex, [Co(N4Ph2)(tBuPNP)], whose bond metrics were most consistent with an anionic Ph2N4 ligand. Density Functional Theory (DFT) investigations of the imido and tetrazido species suggest that they adopt a ground state best described as possessing a low-spin cobalt(II) ion ferromagnetically coupled to an iminyl radical. [ABSTRACT FROM AUTHOR]

We synthesised a sequence of structurally related copper(II) complexes of Schiff base ligands, 2-[(2-benzylamino-ethylimino)-methyl]-phenol [L1(H)], 2-[(2-benzylamino-ethylimino)-methyl]-4-methyl-phenol [L2(H)], and 2-[(2-benzylamino-ethylimino)-methyl]-4-bromo-phenol [L3(H)]. The complexes were characterized by ATR, UV-vis, EPR, ESI-MS, single crystal XRD, and elemental analyses. Based on the crystal structure, the ligand was coordinated to the copper(II) centre in a tridentate mode through phenolate(oxygen), imine nitrogen and amine nitrogen in an NNO fashion and the azide moiety served as an auxiliary ligand. Furthermore, we have investigated the antimicrobial activities of copper(II) complexes against clinically relevant fungal strains, including Candida albicans, Candida glabrata, and Candida tropicalis, as well as bacteria such as Pseudomonas aeruginosa and methicillin-resistant Staphylococcus aureus (MRSA), representing Gram-negative and Gram-positive pathogenic strains. Comparing the activity of complex 2 (128–512 μg mL−1) to complex 3 (64–128 μg mL−1), the latter demonstrated more potent effectiveness against all of the tested fungal strains. The activity of the complexes against MRSA reveals the inhibitory concentrations of 1024 μg mL−1 for 1, 128 μg mL−1 for 2, and 256 μg mL−1 for 3. It is worth mentioning that, at their minimum inhibitory concentrations (MICs), the complexes are not toxic to Galleria mellonella. Furthermore, the spot and broth microdilution assay results were in good agreement with the actual metabolic viability of bacterial and fungal strains, in which the complexes were active while having no effect on the metabolite resazurin. Additionally, in silico studies have been employed to elucidate both non-bonding interactions and the mode of action across protein sequences of experimentally studied microbes. The performance of complexes closely mirrored the reactivity order determined in in vitro studies. The impeding properties of complexes can be due to the dysfunctioning of virulent genes and signalling proteins and also affect the activities of transferase and transcriptase proteins. Overall, the complexes are promising candidates for antimicrobial drug development. We anticipate utilising these molecules for clinical purposes. [ABSTRACT FROM AUTHOR]

A series of non-innocent halogen substituted Schiff base vanadium catecholates were added with different electron donating and withdrawing substituents on the catecholates to investigate the electronic effects on the properties of this class of compounds. We hypothesized that the electronic changes would be reflected in their redox properties and stabilities, which should lead to differences in their biological properties. Using UV-spectroscopy, we measured their hydrolytic stability, and using electrochemistry, we characterized their redox properties. Adding one substituent on the catecholate group on the complexes changed the redox potentials of the complexes; however, less impact on the hydrolytic stability was observed. We discovered that hydrolytic stability was crucial to the anti-proliferative effects on glioblastoma cells, and most of these compounds had effects similar to vanadates regardless of their different redox properties. Hence, we could not determine the importance of changing the electronic properties and redox potential on the anti-proliferative effects of mono-substituted catecholates. However, the studies did show that the pKa of the substituted catecholate showed a linear correlation with the redox potential of the non-innocent Schiff base vanadium complexes, which will be important in future investigations into this class of complexes. [ABSTRACT FROM AUTHOR]

DNA being the necessary element in cell regeneration, controlled cellular apoptosis via DNA binding/cleaving is considered an approach to combat cancer cells. The widely prescribed metallodrug cisplatin has shown interactions with the guanine-N7 center, and a plethora of complexes are continually developed to enhance crosslinking properties as well as covalent and non-covalent interactions. Two pentadentate ligands, L1 (1-(6-(1H-benzo[d]imidazol-2-yl)pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine) and L2 (1-(6-(1-methyl-1H-benzo[d]imidazol-2-yl)pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine), were synthesized together with their respective copper(II) complexes [1](ClO4)2 and [2](ClO4)2, which crystallized in a trigonal bipyramidal fashion. Different analytical and spectroscopic methods confirmed their formation, and their redox behaviour was also examined. The interactions of salmon sperm DNA (ss-DNA) with these two complexes were explored using absorbance spectroscopy, and they both exhibited a binding affinity (Kb) of ∼104 M−1. Fluorescence quenching experiments with ethidium bromide (EB)-bound DNA (EB–DNA) were also performed, and Stern–Volmer constant (KSV) values of 6.93 × 103 and 2.34 × 104 M−1 for [1](ClO4)2 and [2](ClO4)2, respectively, were obtained. Furthermore, DNA conformational changes due to the interactions of both complexes were validated via circular dichroism. We also assessed the DNA cleavage property of these complexes, which resulted in the linearization of circular plasmid DNA. This finding was supported by studying the growth of MDA-MB-231 breast cancer cells upon treatment with both Cu(II) complexes; IC50 values of 5.34 ± 1.02 μM and 0.83 ± 0.18 μM were obtained for [1](ClO4)2 and [2](ClO4)2, respectively. This validates their affinity towards DNA, and these insights can be further utilized for non-platinum based economical metallodrug development based on first row transition metals. [ABSTRACT FROM AUTHOR]

The syntheses, structures, luminescence and magnetic properties of a new series of Ln(III) complexes of the formula [Ln(L)(H2O)2(DMF)2][Ln(L)2] (in which H2L is N,N′-ethylaminebis[1-phenyl-3-methyl-4-formylimino-2-pyrazoline-5-one]; Ln(III) – Gd (1), Tb (2), or Dy (3) ions). The crystal structures were determined by single-crystal X-ray diffraction measurements for all the above-mentioned complexes. The crystals of these compounds consist of cationic [Ln(L)(H2O)2(DMF)2]+ and anionic [Ln(L)2] moieties which form a 3D supramolecular architecture by the H-bonds and electrostatic forces. Luminescence emission in the visible range was observed for Tb(III) and Dy(III) compounds upon ligand sensitization, with moderate quantum yields of 3.2% for the Dy complex and 24.2% for the Tb analogue. Moreover the Tb(III) complex demonstrates triboluminescence activity. The dynamic magnetization studies revealed that 1 and 2 demonstrate field-induced magnetic relaxation with effective energy barriers, ΔE‖kB = 24 K (for 1) and 85 K (for 2), while the Dy complex 3 exhibits slow relaxation of magnetization in zero field with an activation energy of 256 K. [ABSTRACT FROM AUTHOR]

In the present era, the fixation of atmospheric CO2 is of significant importance and plays a crucial role in maintaining the balance of carbon and energy flow within ecosystems. Generally, CO2 fixation is carried out by autotrophic organisms; however, the scientific community has paid substantial attention to execute this process in laboratory. In this report, we synthesized two carbonato-bridged trinuclear copper(II) complexes, [Cu3(L1)3(μ3-CO3)](ClO4)3 (1) and [Cu3(L2)3(μ3-CO3)](ClO4)3 (2) via atmospheric fixation of CO2 starting with Cu(ClO4)2·6H2O and easily accessible pyridine/pyrazine-based N4 donor Schiff base ligands L1 and L2, respectively. Under very similar reaction conditions, the ligand framework embedded with the phenolate moiety (HL3) fails to do so because of the reduction of the Lewis acidity of the metal center, inhibiting the formation of a reactive hydroxide bound copper(II) species, which is required for the fixation of atmospheric CO2. X-ray crystal structures display that carbonate-oxygen atoms bridge three copper(II) centers in μ3syn–anti disposition in 1 and 2, whereas [Cu(HL3)(ClO4)] (3) is a mononuclear complex. Interestingly, we also isolated an important intermediate of atmospheric CO2 fixation and structurally characterized it as an anti–anti μ2 carbonato-bridged dinuclear copper(II) complex, [Cu2(L2)2(μ2-CO3)](ClO4)2·MeOH (2-I), providing an in-depth understanding of CO2 fixation in these systems. Variable temperature magnetic susceptibility measurement suggests ferromagnetic interactions between the metal centers in both 1 and 2, and the results have been further supported by DFT calculations. The catalytic efficiency of our synthesized complexes 1–3 was checked by means of catechol oxidase and phenoxazinone synthase-like activities. While complexes 1 and 2 showed oxidase-like activity for aerobic oxidation of o-aminophenol and 3,5-di-tert-butylcatechol, complex 3 was found to be feebly active. ESI mass spectrometry revealed that the oxidation reaction proceeds through the formation of complex–substrate intermediations and was further substantiated by DFT calculations. Moreover, active catalysts 1 and 2 were effectively utilized for the base-free oxidation of benzylic alcohols in the presence of air as a green and sustainable oxidant and catalytic amount of TEMPO in acetonitrile. Various substituted benzylic alcohols smoothly converted to their corresponding aldehydes under very mild conditions and ambient temperature. The present catalytic protocol showcases its environmental sustainability by producing minimal waste. [ABSTRACT FROM AUTHOR]

A thiophene-derived Schiff base ligand (E)-2-morpholino-N-(thiophen-2-ylmethylene)ethanamine was used for the synthesis of M(II) complexes, [TEM(M)X2] (M = Co, Cu, Zn; X = Cl; M = Cd, X = Br). Structural characterization of the synthesized complexes revealed distorted tetrahedral geometry around the M(II) center. In vitro investigation of the synthesized ligand and its M(II) complexes showed considerable anti-urease and leishmanicidal potential. The synthesized complexes also exhibited a significant inhibitory effect on urease, with IC50 values in the range of 3.50–8.05 μM. In addition, the docking results were consistent with the experimental results. A preliminary study of human colorectal cancer (HCT), hepatic cancer (HepG2), and breast cancer (MCF-7) cell lines showed marked anticancer activities of these complexes. [ABSTRACT FROM AUTHOR]

A Zn(II) coordination polymer (CP), namely, {[Zn(DTPB)]·DMF}n (H2DTPB = 1-(3,5-di(2H-tetrazol-5-yl)phenyl)-1H-benzeimidazole, Zn-DTPB), was assembled from a new tetrazolyl–benzimidazolyl heterotopic triangular ligand. In Zn-DTPB, the tetrazolyl groups connect the Zn(II) ions into a 2D network with a (4·82) topology, and the 2D network is further interconnected by Zn–N bonds between Zn(II) and benzimidazolyl groups to a 3D framework featuring a 4-connected sra topology. The DMF molecules were tightly encapsulated in the framework and could not be released until the framework decomposed. The framework is stable up to 300 °C and can be retained in water for 72 h. The luminescence in the solid-state and in various solvents was investigated, implying that Zn-DTPB can be used to detect acetone and triethylamine (TEA) in water by fluorescence quenching with good sensitivity and selectivity. Moreover, Zn-DTPB exhibited excellent reproducibility in sensing acetone. Mechanistic studies have shown that the fluorescence quenching of acetone and triethylamine is caused by competitive absorption and structural amorphization, respectively. Interestingly, the amorphous product can be transformed into Zn-DTPB crystals through a solvent-media structural transformation process. [ABSTRACT FROM AUTHOR]

Four new tetradentate Schiff-base ligands were prepared in situ from the 1 : 2 condensation of 1,3-diaminopropane and either 2-thiazolecarboxaldehyde (L2thiazole), 4-thiazolecarboxaldehyde (L4thiazole), 4-oxazolecarboxaldehyde (L4oxazole), or 5-bromopyridine-2-aldehyde (L5Br-pyridine), and complexed with [Fe(NCS)2(pyridine)4] to give four monometallic FeII complexes, [Fe(Lheterocycle)(NCS)2]. Structural characterisation shows the expected octahedral FeII centres in all cases, with Lheterocycle occupying the equatorial plane and the two thiocyanate ligands trans to each other, resulting in an N6 coordination sphere. Solid state magnetic measurements showed that the two complexes with the thiazole-based ligands exhibit the beginning of a spin transition above 300 K, with T1/2 = 350 K for [Fe(L4thiazole)(NCS)2] and 400 K for [Fe(L2thiazole)(NCS)2], whereas the 4-oxazole-based ligand gives [Fe(L4oxazole)(NCS)2] which remains high spin at all measured temperatures (50–400 K). Interestingly, [Fe(L5Br-pyridine)(NCS)2] crystallised as two solvent-free polymorphs: magnetic measurements on samples with both polymorphs present showed a two step SCO with an abrupt transition at T1/2 = 245 K assigned to the transition in polymorph A (as this was also seen in a sample of pure polymorph A), and a gradual transition at T1/2 = 304 K assigned to polymorph B. These findings show that the order of increasing ligand field strength for these heterocycles is 4-oxazole ≪ 5Br-pyridine < 4-thiazole < 2-thiazole. [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]