Coloring–decoloring behavior of fluoroalkyl end‐capped 2‐acrylamido‐2‐methylpropanesulfonic acid oligomer/acetone composite in methanol

A reddish‐brown fluoroalkyl end‐capped 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) oligomer/acetone composite was prepared by heating the white oligomer powder with acetone at 80 °C for 3 h. The color was not observed in the corresponding non‐fluorinated AMPS oligomer/acetone composite, which was prepared under similar conditions. The coloring was probably caused by the formation of acetone polyaldol condensation products in the fluorinated oligomeric gel network cores. The colored R_F‐(AMPS)_n‐R_F/acetone composite powders were stable and did not exhibit any color change after 2 years in natural light at room temperature. The colored composite powders dissolved in methanol to give a reddish‐brown solution at room temperature. However, the retro‐polyaldol condensation decolored the solution after 1 day at room temperature. This is the first example of the retro‐aldol polycondensation of acetone under mild conditions. The decoloration increased by between 38‐ and 70‐fold under UV irradiation, compared with that in dark conditions. The coloring–decoloring behavior was consistent and repeatable; therefore our fluorinated oligomer/acetone composites are promising candidates for new fluorinated coloring materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2555–2564     

Crystallisation of nematic liquid crystal mixtures

In this paper, we propose a method to accelerate the crystallisation of nematic liquid crystal mixtures based on crystallisation theory. This method is to hold a nematic liquid crystal sample at a temperature suitable for crystal growth after aging it at a temperature suitable for nucleation. After we specified these temperatures of a nematic liquid crystal mixture using differential scanning calorimetry, we demonstrate that the two-temperature aging method is effective for the crystallisation of other nematic liquid crystal mixtures in which the crystal-liquid crystal transition temperature has so far been undetectable.     

Synthesis and smectogenic properties of novel phloroglucinol-based star-shaped liquid crystals containing three peripheral alkyloxylated Schiff base arms

A series of symmetrical trimeric liquid crystalline compounds of which the molecular structure with a central core of 1,3,5-benzene attached by three rod-like mesogenic Schiff base moieties via the propylene spacers and ether linkages has successfully been synthesised and characterised by infra red and nuclear magnetic resonance spectroscopic techniques. All the star-shaped compounds in this series exhibit predominantly SmC phase except the analogue possessing terminal C₈H₁₇ group. It is apparent that the members with even parity from C₁₀H₂₁ to C₁₆H₃₃ show enantiotropic SmC phase while the member with longest terminal chain of C₁₈H₃₇ is inclined to monotropic smectogen. The X-ray diffraction measurements reveal that the tilted smectic layer structures of the SmC phase are confirmed to have an obvious sharp peak at small angles of 2θ ～ 1.03°–1.48° with d-spacing values of 4.01–4.58 nm, which are corresponding to tilt angles of ～48° in the SmC phase.     

New heterocyclic metallomesogens: synthesis,mesomorphic and thermal behaviours of Cu(II) complexes with 1,2,3-triazole-based Schiff bases ligands

Two series of new Cu(II) complexes derived from the reaction of copper acetate with the non-linear 1,2,3-triazole-based Schiff bases have successfully been synthesised. The structures of the ligands and its complexes were elucidated by elemental analysis, FT-IR, ¹H-NMR and UV–visible spectroscopic techniques. The differential scanning calorimetry and polarizing optical microscopy supported the anisotropic properties of uncoordinated ligands in which the focal conic fan-shaped texture and/or broken fan-shaped texture characteristics of respective SmA and SmC phases were recorded. However, not all of their corresponding Cu(II) complexes are mesogenic. Although the iodo-substituted ligands with even parity C₁₀H₂₉ to C₁₄H₃₃ are non-stable and exhibit SmA phase which is not reproducible, the ultimate Cu(II) complexes show exclusively stable SmA phase. This observation can be ascribed to the enhanced colinearity and molecular anisotropic by the presence of Cu-N and Cu-O coordination modes. On the other hand, the comparison studies show that different positions of ortho-hydroxyl group affect the mesomorphic and thermal behaviour of ligands and Cu(II) complexes.     

Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates

The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)₃L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams.     

Divergent and Chemoselective Transformations of Thioamides with Designed Carbene Equivalents

The reactions of thioamides with ortho-nitro-substituted iodonium ylides proceeded under mild conditions to give enaminones or thiazoles, depending on the iodonium ylide used. This protocol allowed the use of protic solvents, including aqueous solutions, and therefore coupling reactions with complex molecules such as peptides or steroids were possible. A mild and efficient method for the synthesis of various iodonium ylides was established. DFT calculations suggested that the halogen bonding between a thioamide and iodonium ylide was important in this chemoselective coupling reaction. The potential use of enaminones conjugated with pharmaceuticals as prodrugs was also demonstrated.     

Synthesis, Characterization, and Crystal Structure of a (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) Complex with a Dinucleating Hexapyridine Ligand, 1,2-Bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane. The First Example of a Discrete (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) Complex with a Dinucleating Ligand

A mononucleating tripyridine ligand, 2-(bis(2-pyridyl)methyl)-6-methylpyridine (L(1)), and a dinucleating hexapyridine ligand, 1,2-bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane (L(2)), have been prepared. The reaction of a carbanion of 2,6-lutidine with 2-bromopyridine affords L(1) which is converted to L(2) quantitatively by treating with tert-butyllithium and 1,2-dibromoethane. (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) complexes [Fe(2)(O)(OAc)(2)(L(1))(2)](ClO(4))(2) (1) and [Fe(2)(O)(OAc)(2)L(2)](ClO(4))(2) (2) have been synthesized and characterized by means of infrared, UV/vis, mass, and M?ssbauer spectroscopies and by measuring magnetic susceptibility and cyclic voltammograms. All the spectral data are consistent with the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure in both 1 and 2. A relatively strong molecular ion peak at m/z 865 corresponding to [{Fe(2)O(OAc)(2)L(2)}(ClO(4))](+) in a FAB mass spectrum of 2 suggests the stabilization of the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure by L(2) in a solution state. The compound 2.DMF.2-PrOH.H(2)O, chemical formula C(44)Cl(2)Fe(2)H(51)N(7)O(16), crystallizes in the monoclinic space group C2/c with a = 22.034(6) ?, b = 12.595(5) ?, c = 20.651(7) ?, beta = 121.49(2) degrees, and Z = 4. The cation has 2-fold symmetry with the bridging oxygen atom on the 2-fold axis: Fe-(&mgr;-O) = 1.782(5) ?, Fe-O-Fe = 123.6(6) degrees, and Fe.Fe = 3.142(3) ?. The diiron(III) core structure of 2 seems to be stabilized by encapsulation of the ligand. Compound 2 is the first example of a discrete (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) complex with a dinucleating ligand.     

1,2,4-triazines. III. A convenient and general synthesis of 4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-ones

4H-[1,3,4]Thiadiazolo[2,3-c][1,2,4]triazin-4-ones were prepared by cyclization of 3-thio-4-amino-1,2,4-tri-azine-3,5(2H,4H)-diones with a variety of acids in the presence of concentrated sulfuric acid. The synthesis appears to be general.     

Weighted Counting of Inversions on Alternating Sign Matrices

We generalize the author’s formula (2011) on weighted counting of inversions on permutations to one on alternating sign matrices. The proof is based on the sequential construction of alternating sign matrices from the unit matrix which essentially follows from the earlier work of Lascoux-Schützenberger (1996).

     

Stable rigged configurations for quantum affine algebras of nonexceptional types

For an affine algebra of nonexceptional type in the large rank we show the fermionic formula depends only on the attachment of the node 0 of the Dynkin diagram to the rest, and the fermionic formula of not type A can be expressed as a sum of that of type A with Littlewood–Richardson coefficients. Combining this result with Kirillov et al. (2002) [13] and Lecouvey et al. (2011) [18] we settle the X=M conjecture under the large rank hypothesis.