π-π Stacking and Magnetic Coupling Mechanism on a Mono-nuclear Mn(Ⅱ) Complex

A new mono-nuclear Mn(Ⅱ) complex [Mn(MPT)2(NCS)(HOCH3)]ClO4(MPT = 2-methoxyl-1,10-phenanthroline) has been synthesized with 2-methoxyl-1,10-phenanthroline and thiocyanate anion as ligands,and its crystal structure was determined by X-ray crystallography.The crystal data:monoclinic system,space group P21/c with a = 12.8849(17),b = 15.684(2),c = 14.2703(19) ,β = 92.126(2)°,V = 2881.9(7) 3,Z = 4,C28H24ClMnN5O7S,Mr = 664.97,Dc = 1.533 g/cm3,F(000) = 1364 and μ = 0.679 mm-1.In the crystal,MPT functions as a bidentate ligand and Mn(Ⅱ) ion assumes a distorted octahedral geometry.In the crystal there are two types of π-π stacking interactions among the adjacent complexes,which involves 1,10-phenanthroline rings.The theoretical calculations reveal that the two types of π-π stacking resulted in a weak anti-ferromagnetic coupling with 2J =-14.68 cm-1 and a weak ferromagnetic coupling with 2J = 0.70 cm-1,respectively.The theoretical calculations also reveal that there are both spin polarization and spin delocalization in the two π-π stacking systems,and the magnetic coupling signs are unable to explain with McConnell I spin-polarization mechanism.     

Ring-Opening Polymerization of γ-(4-Vinylbenzyl)-(L)-Glutamate N-Carboxyanhydride for the Synthesis of Functional Polypeptides

Introducing various pendant functional groups and building blocks of interest to polypeptides in a highly efficient, controlled manner is crucial to access polypeptide materials with desired structures and functions. In this study, we synthesized γ-(4-vinylbenzyl)-(L)-glutamate N-carboxyanhydride (VB-Glu-NCA), which was readily obtained and purified in large quantity. VB-Glu-NCA monomer was subsequently used for the synthesis of polypeptides containing conjugation-amenable, pendant vinyl functional groups. Controlled, living polymerizations of VB-Glu-NCA were achieved by using hexamethyldisilazane (HMDS) as the initiator, catalytic amounts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the co-catalyst, and nitrobenzene as the inhibitor of radical-induced side reactions on the vinyl group of VB-Glu-NCA. The resulting poly(γ-(4-vinylbenzyl)-(L)-glutamate) (PVBLG) gave rise to polypeptides containing pendant functional groups or moieties through various vinyl chemistries.     

Synthesis and characterization of hyperbranched polystyrene via click reaction of AB2 macromonomer

Well‐defined hyperbranched polystyrenes have been successfully prepared by polymerization of AB₂ macromonomer, polystyrene containing an azide group at its one end and two terminal propargyl groups at the other end via click reaction. For preparation of AB₂ macromonomers, an ATRP initiator, bispropargyl 2‐bromosuccinate (BPBS) with two propargyl groups and one bromine group was synthesized by the successive bromination and esterification reaction of L ‐aspartic acid. The resulting BPBS initiated the ATRP of St, and subsequently, the terminal bromine groups of (CH≡C)₂‐PS‐Brs were substituted by N₃ via the reaction with sodium azide resulting the AB₂ macromonomer, (CH≡C)₂‐PS‐N₃ with various molecular weights. All intermediates and the resultant polymers were characterized by GPC, ¹H NMR, FTIR, and MALLS methods. The polymerization kinetics study showed fast increase of DP at the initial stage of polymerization and then slow increase of their DP. The final “HyperMacs” have high‐molecular weight up to M_w,MALLS = 340,000 g/mol, their molecular weight distributions were moderately narrow (M_w/M_n = 1.47–1.65). The ratios of [η]_H/[η]_L of the HyperMacs formed in the polymerization system increased with evolution of polymerization. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 454–462, 2010     

Synthesis and Effect of Cation Binding on Photophysical Properties of 1,8-Anthraceno-18-Crown-5

ThesystemsconsistingofafluorophorelinkedtoacrownethermoietyareeXtensivelyinvestigated'-'.Sincedrasticchangesintheirphotophysicalpropertiescanbeobservedbycomplexationwithion,theycanbeusedforionicdetection"'.Recentreportsfocusonazamacrocyclicderivativeswithfluorophores"',inwhichthefluorophoreandcrownethermoietywerelinkedvianitrogenatom.Thepresenceofabasicnitrogenatomwhichiseasytobeprotonatedleadstoelthancementoffluorescencequantumyield""'.Wereplacedthenitrogenatomofthecrownbyoxygenwhichisexpect…     

Pressure driven transport of glassy solid helium in cylindrical nanopores at very low temperature regime

By using the glassy helium model and boundary perturbation method, we can obtain the velocity fields (as well as the flow rate up to the second order) at very low temperature regime inside the wavy‐rough cylindrical nanopores. Our results show that the velocities of solid helium reported before by many groups could be reproduced by carefully selecting relevant physical parameters.     

Synergistic Effect of Oxalate and Ethylene Glycol on the Formation of SnO2 Rods

SnO₂ rods have been synthesized by using tin (II) chain‐like complexes as precursors in which oxalate and ethylene glycol act as co‐ligands. On the basis of experimental analysis, a reasonable formation mechanism of rods is discussed, which is further supported by Fourier transform infrared spectroscopy (FT‐IR). These results show that the synergistic effect of oxalate group and ethylene glycol plays an important role in the formation of long SnO₂ rods.     

Configuration and conformation of taibaihenryiin T isolated from <Emphasis Type="Italic">Phlomis umbrosa</Emphasis>

Taibaihenryiin T was isolated for the first time from Phlomis umbrosa Turcz, and its structure was elucidated on the basis of IR and NMR spectra analysis. Its molecular configuration, conformation, and crystal structure were also characterized by X-ray structure analysis. The infrequency of the C–O–O–C group is manifested in this molecular configuration, and hydrogen bonding assembles the molecules into a three-dimensional networking structure in the crystal.     

A New Dimeric Alkaloid from the Leaf of Psychotria calocarpa

Psychotriasine was isolated from the leaves of Psychotria calocarpa (Rubiaceae). The structure was established by spectroscopic methods including 2D‐NMR analysis. To the best of our knowledge, psychotriasine is the first example of a dimeric tryptamine‐related alkaloid that contains a free N^α‐methyltryptamine unit in the molecule.