Syntheses and structures of three macrocyclic supramolecular complexes and one ZnII-containing coordination polymer generated from a semi-rigid multidentate N-containing ligand

Semirigid organic ligands can adopt different conformations to construct coordination polymers with more diverse structures when compared to those constructed from rigid ligands. A new asymmetric semirigid organic ligand, 4-{2-[(pyridin-3-yl)methyl]-2H-tetrazol-5-yl}pyridine (L), has been prepared and used to synthesize three bimetallic macrocyclic complexes and one coordination polymer, namely, bis(μ-4-{2-[(pyridin-3-yl)methyl]-2H-tetrazol-5-yl}pyridine)bis[dichloridozinc(II)] dichloromethane disolvate, [Zn2Cl4(C12H10N6)2]·2CH2Cl2, (I), the analogous chloroform monosolvate, [Zn2Cl4(C12H10N6)2]·CHCl3, (II), bis(μ-4-{2-[(pyridin-3-yl)methyl]-2H-tetrazol-5-yl}pyridine)bis[diiodidozinc(II)] dichloromethane disolvate, [Zn2I4(C12H10N6)2]·2CH2Cl2, (III), and catena-poly[[[diiodidozinc(II)]-μ-4-{2-[(pyridin-3-yl)methyl]-2H-tetrazol-5-yl}pyridine] chloroform monosolvate], {[ZnI2(C12H10N6)]·CHCl3} n , (IV), by solution reaction with ZnX 2 (X = Cl and I) in a CH2Cl2/CH3OH or CHCl3/CH3OH mixed solvent system at room temperature. Complex (I) is isomorphic with complex (III) and has a bimetallic ring possessing similar coordination environments for both of the ZnII cations. Although complex (II) also contains a bimetallic ring, the two ZnII cations have different coordination environments. Under the influence of the I− anion and guest CHCl3 molecule, complex (IV) displays a significantly different structure with respect to complexes (I)–(III). C—H...Cl and C—H...N hydrogen bonds, and π–π stacking or C—Cl...π interactions exist in complexes (I)–(IV), and these weak interactions play an important role in the three-dimensional structures of (I)–(IV) in the solid state. In addition, the fluorescence properties of L and complexes (I)–(IV) were investigated.

Hydrothermal Synthesis of Hydroxyapatite Assisted by Gemini Cationic Surfactant

Hydroxyapatite (HAp) has been synthesized by a hydrothermal treatment in the presence of a Gemini cationic surfactant. This process is a new strategy of synthesis and mainly consists of two parts, i.e., an ordinary hydrothermal treatment and a liquid-solid-solution reaction (LSS strategy). Crystalline HAp nanorods or nanogranules with length of 50-180 nm and width of 30-40 nm were produced by ordinary hydrothermal treatment. By contrary, HAp spheres with a 3D architecture were fabricated with Gemini cationic surfactant by LSS strategy. For Gemini cationic surfactant concentration of 0.05%, spherical HAp particles with an average diameter of 1.7 μm were obtained.

ON THE THERMODYNAMICS OF ANTIOXIDANT ACTION OF NATURALLY OCCURRING HYDROXYDERIVATIVES OF CIS-CINNAMIC ACID

Antioxidant activity represents one of the important features of phenolic acids, such as hydroxyderivatives of cinnamic acid. However, in the case of cis-cinnamic acid derivatives, corresponding thermochemistry data can be still considered scarce. This work is focused on the two most relevant mechanisms of primary antioxidant action in gas-phase, non-polar benzene and in aqueous solution. Reaction enthalpies describing thermodynamics of Hydrogen Atom Transfer (HAT) and Sequential Proton-Loss – Electron Transfer (SPLET) mechanisms were theoretically investigated using (SMD) M06-2X/6-311++G(d,p) method for cis-ortho-coumaric, cis-meta-coumaric, cis-para-coumaric, cis-ferulic, cis-sinapic and cis-caffeic acid and their carboxylate anions. The effect of carboxyl COOH group deprotonation on the thermodynamics of studied mechanisms was assessed for the three environments.

Nano MnO2 Radially Grown on Lignin-Based Carbon Fiber by One-Step Solution Reaction for Supercapacitors with High Performance

MnO2-deposited lignin-based carbon fiber (MnO2-LCF) mats are fabricated for supercapacitor applications. LCF mats are produced from alkali lignin via electrospinning followed by stabilization and carbonization. The carbonization process is carried out at 800, 900, and 1000 °C, and the corresponding mats are denoted as MnO2-LCF-800, MnO2-LCF-900, and MnO2-LCF-1000, respectively. The LCF mats are immersed in a KMnO4 solution at room temperature for 72 h to obtain MnO2-LCF mats. The scanning electron microscopy and X-ray diffraction analysis confirm the deposition of MnO2 on the LCFs. The Brunauer–Emmett–Teller analysis, X-ray spectroscopy, and Raman spectroscopy reveal that MnO2-LCF-800 mat possesses a large number of mesopores and Mn vacancies as compared to MnO2-LCF-900 mat and MnO2-LCF-1000 mat. Consequently, MnO2-LCF-800 mat possesses the best electrochemical properties with a specific capacitance of 131.28 F∙g−1, an energy density of 14.77 Wh∙kg−1, and a power density of 135.01 W∙kg−1 at a specific current of 0.3 A∙g−1. Hence, MnO2-LCF-800 mat shows high potential to be used as a high-performance supercapacitor.

Acidity Suppression of Hole Transport Layer via Solution Reaction of Neutral PEDOT:PSS for Stable Perovskite Photovoltaics

Poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS) is typically used for hole transport layers (HTLs), as it exhibits attractive mechanical, electrical properties, and easy processability. However, the intrinsically acidic property can degrade the crystallinity of perovskites, limiting the stability and efficiency of perovskite solar cells (PSCs). In this study, inverted CH3NH3PbI3 photovoltaic cells were fabricated with acidity suppressed HTL. We adjusted PEDOT:PSS via a solution reaction of acidic and neutral PEDOT:PSS. And we compared the various pH-controlled HTLs for PSCs devices. The smoothness of the pH-controlled PEDOT:PSS layer was similar to that of acidic PEDOT:PSS-based devices. These layers induced favorable crystallinity of perovskite compared with acidic PEDOT:PSS layers. Furthermore, the enhanced stability of pH optimized PEDOT:PSS-based devices, including the prevention of degradation by a strong acid, allowed the device to retain its power conversion efficiency (PCE) value by maintaining 80% of PCE for approximately 150 h. As a result, the pH-controlled HTL layer fabricated through the solution reaction maintained the surface morphology of the perovskite layer and contributed to the stable operation of PSCs.