Discotic liquid crystals of transition metal complexes 46: mesomorphism and antagonist solubility of octaphenoxy-phthalocyaninato copper(II) complex substituted by oligoether chains

2012 ◽  
Vol 16 (11) ◽  
pp. 1209-1216 ◽  
Author(s):  
Hiroyuki Sato ◽  
Yuya Sakagami ◽  
Eiji Itoh ◽  
Kazuchika Ohta
Keyword(s):  
Liquid Crystalline ◽  
Polar Solvent ◽  
Optical Microscope ◽  
Discotic Liquid Crystals ◽  
X Ray Diffraction ◽  
Temperature Dependent ◽  
Polar Solvents ◽  
X Ray ◽  
Virgin Sample ◽  
Liquid Crystalline Compound

We synthesized a novel discotic liquid crystalline compound, octakis[3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenoxy]phthalocyaninato copper(II) (abbreviated as [m- MeO(EtO)3PhO]8PcCu ), and established the mesomorphism by using a differential scanning calorimeter, a polarizing optical microscope, and temperature-dependent wide angle X-ray diffraction diffractometer. Very interestingly, this [m- MeO(EtO)3PhO]8PcCu complex showed a hexagonal ordered columnar (Colho) mesophase in the virgin sample, whereas it showed a rectangular ordered columnar (Colro(P21/a)) mesophase in the non-virgin sample. The Colho mesophase gave a dimer stacking distance at 9.26 Å, whereas the Colro mesophase gave a short monomer stacking distance at 3.45 Å. Furthermore, this novel Pc derivative is readily soluble in polar solvents such as acetone, ethanol and methanol. Using antagonist solubilities of the present hydrophilic [m- MeO(EtO)3PhO]8PcCu derivative in a polar solvent and the previous hydrophobic (C10O)16TzCu derivative in the non-polar solvent, a p-n junction layered thin films could be successfully prepared.

Discotic liquid crystals of transition metal complexes: 28. Temperature-dependent electronic spectra and X-ray structural analysis of discotic liquid crystalline bis(octakisdodecyloxyphthalocyaninato)lutetium(III) complex

2001 ◽  
Vol 05 (01) ◽  
pp. 44-50 ◽  
Author(s):  
RIE NAITO ◽  
KAZUCHIKA OHTA ◽  
HIROFUSA SHIRAI
Keyword(s):  
Thin Film ◽  
Phase Transitions ◽  
Structural Analysis ◽  
Transition Metal Complexes ◽  
Electronic Spectra ◽  
Liquid Crystalline ◽  
Discotic Liquid Crystals ◽  
X Ray Diffraction ◽  
Temperature Dependent ◽  
X Ray

An unidentified mesophase D x of bis(octakisdodecyloxyphthalocyaninato)lutetium(III) reported by us in 1997 was reinvestigated by temperature-dependent X-ray diffraction and temperature-dependent electronic spectra of the thin film. The D x phase was thus established as a novel type of D ro (P21/a) mesophase in which two different stacking distances ht and hf exist. It was also revealed that the step-up increase of electroconductivity is attributable to the step-up enlargement of π-π overlap of Pc macrocycles according to the phase transitions crystal → D ro (P21/a) → D ho . This is strongly related to delocalization of the radical electron.

Liquid crystalline polyureas with oligo(ethylene glycol) sequences

e-Polymers ◽  
2010 ◽  
Vol 10 (1) ◽  
Author(s):  
Shahram Mehdipour-Ataei ◽  
Leila Akbarian-Feizi
Keyword(s):  
Liquid Crystalline ◽  
Spectroscopic Method ◽  
Polymerization Reaction ◽  
X Ray Diffraction ◽  
Subsequent Reaction ◽  
Scanning Calorimetry ◽  
Polar Solvents ◽  
X Ray ◽  
H Nmr ◽  
Ft Ir

AbstractA diamine monomer containing ester, amide and ether functional groups was prepared and its polymerization reaction with different diisocyanates to give main chain poly(ester amide ether urea)s was investigated. The monomer was synthesized via reaction of terephthaloyl chloride with 4-hydroxybenzoic acid and subsequent reaction of the resulted diacid with 1,8-diamino-3,6-dioxaoctane. The polymers were characterized by FT-IR and 1H-NMR spectroscopic method and elemental analysis. The resulting polymers exhibited excellent solubility in polar solvents. Crystallinity of the resulted polymers was evaluated by wide-angle X-ray diffraction (WXRD) method, and they exhibited semi-crystalline patterns. The glass transition temperatures (Tg) of the polymers determined by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) were in the range of 88-112 °C. The temperatures for 10% weight loss (T10) from their thermogravimetric analysis (TGA) curves were found to be in the range of 297-312 °C in air. Also the prepared polyureas showed liquid crystalline character.

Structural analysis by X-ray diffraction of a non-polar alkenyl liquid crystalline compound

1996 ◽  
Vol 20 (6) ◽  
pp. 765-770 ◽  
Author(s):  
A. Nath ◽  
S. Gupta ◽  
P. Mandal ◽  
S. Paul ◽  
H. Schenk
Keyword(s):  
Structural Analysis ◽  
Liquid Crystalline ◽  
Crystalline Compound ◽  
X Ray Diffraction ◽  
X Ray ◽  
Liquid Crystalline Compound

scholarly journals Discotic Liquid Crystals Based on Cu(I) Complexes with Benzoylthiourea Derivatives Containing a Perfluoroalkyl Chain

2018 ◽  
Vol 2018 ◽  
pp. 1-10
Author(s):  
Monica Iliş ◽  
Viorel Cîrcu
Keyword(s):  
Liquid Crystalline ◽  
Large Temperature ◽  
Discotic Liquid Crystals ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Polarized Optical Microscopy ◽  
X Ray ◽  
Ir And Nmr Spectroscopy ◽  
Hexagonal Columnar ◽  
Mesomorphic Properties

Mesomorphic three-coordinate copper(I) complexes ([Cu(BTU)2X], where X = Cl or Br) based on a new N-benzoylthiourea (BTU) ligand with two decyloxy and one perfluorooctyl groups at its periphery were designed and prepared. The BTU ligand coordinates via the S atom in a neutral monodentate fashion as confirmed by IR and NMR spectroscopy data. The liquid crystalline behavior of these copper(I) complexes was investigated by a combination of polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction analysis (XRD), while their thermal stability was studied by thermogravimetric analysis (TGA). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100°C.

Chiral Liquid Crystalline Polymers Containing Isosorbide Groups

2013 ◽  
Vol 781-784 ◽  
pp. 403-406
Author(s):  
Mei Tian ◽  
Zhi Xin Xu ◽  
Li Gao ◽  
Dan Shu Yao ◽  
Xiao Zhi He ◽  
...  
Keyword(s):  
Liquid Crystal ◽  
Liquid Crystalline ◽  
Main Chain ◽  
Liquid Crystalline Polymers ◽  
Optical Microscope ◽  
Liquid Crystal Polymers ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Crystalline Polymers

A series of new main-chain liquid-crystal polymers (LCPs) were prepared from sebacoyl chloride (SD) and various amount of 4, 4-Dihydroxy-2, 2-dimethyl Benzalazine (DDBA) and isosorbide (ISO). The liquid crystal (LC) properties were investigated by polarized optical microscope (POM), differential scanning calorimetry (DSC) and X-ray diffraction measurements. P1 exhibited a typical nematic thread texture, which contains no ISO. P2-P7 are Sc* and N LCPs, which exhibited broken fan-shaped texture and droplet texture. The introduction of chiral units into the polymers led to a change of mesomorphase, as compared with P1.

scholarly journals Discotic liquid crystals of transition metal complexes 51: Synthesis and mesomorphism of flat-pumpkin-shaped phthalocyanine-fullerene dyads

2014 ◽  
Vol 18 (10n11) ◽  
pp. 856-868 ◽  
Author(s):  
Miho Yoshioka ◽  
Kazuchika Ohta ◽  
Yohei Miwa ◽  
Shoichi Kutsumizu ◽  
Mikio Yasutake
Keyword(s):  
Liquid Crystals ◽  
Liquid Crystalline ◽  
Thermal Fluctuation ◽  
Molecular Shape ◽  
Optical Microscope ◽  
Excluded Volume ◽  
Discotic Liquid Crystals ◽  
X Ray ◽  
Donor Acceptor ◽  
Liquid Crystalline Material

We have synthesized a novel type of donor–acceptor liquid crystalline material, phthalocyanine-fullerene ( Pc - C 60) dyad, [m,p,m′-( C 14 O )3 PhO ]6 PcCu - C 60 (7), and the Pc precursors, [m,p,m′-( C 14 O )3 PhO ]6 PcCu - OFBA (6) and [m,p,m′-( C 14 O )3 PhO ]6 PcCu - OH (5), and established their mesomorphism by using a polarizing optical microscope, a differential scanning calorimeter and a small angle X-ray diffractometer. Very interestingly, their corresponding previous parent Pc derivative, [m,p,m′-( C 14 O )3 PhO ]8 PcCu (4), shows a very wide temperature region ca. 90°C of a bicontinuous Cub(Pn3m) mesophase, whereas the present children Pc precursors (5 and 6) and Pc- C 60 dyad 7 show not the Cub mesophase but a Colho mesophase. It is also noteworthy that the staking distance in the Colho mesophase of the Pc- C 60 dyad 7was a very big value of ca. 9.1 Å, which is the biggest in discotic liquid crystals to our best knowledge. It may be originated from the biggest excluded volume caused by thermal fluctuation of peripheral long alkoxy chains at m, m′-positions. The excluded volume caused by thermal fluctuation of the peripheral long chains is so big that the molecular shape of the Pc derivative 4 and the Pc- C 60 dyad 7 very resembles a flat pumpkin.

Discotic liquid crystals of transition metal complexes 44: synthesis of hexaphenoxy-substituted phthalocyanine derivatives showing spontaneous perfect homeotropic alignment

2012 ◽  
Vol 16 (10) ◽  
pp. 1114-1123 ◽  
Author(s):  
Masaaki Ariyoshi ◽  
Makiko Sugibayashi-Kajita ◽  
Ayumi Suzuki-Ichihara ◽  
Takayuki Kato ◽  
Tenpei Kamei ◽  
...  
Keyword(s):  
Differential Scanning Calorimetry ◽  
Liquid Crystals ◽  
Transition Metal ◽  
Transition Metal Complexes ◽  
Discotic Liquid Crystals ◽  
X Ray Diffraction ◽  
Temperature Dependent ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Homeotropic Alignment

We have synthesized novel hexaphenoxy-substituted phthalocyanine derivatives, 2-(12-hydroxydodecyloxy)-3-methoxy-9,10,16,17,23,24-hexakis(3,4-di-n-alkoxyphenoxy)phthalocyaninato copper(II) (abbreviated as Cn(OC12OH)PcCu : n = 10, 12, 14), and investigated their columnar mesomorphism and homeotropic alignment property. These hexaphenoxy-substituted Pc derivatives could be successfully isolated and purified from the mixture products by polarity difference. It was revealed by using polarizing optical microscopic observations, differential scanning calorimetry and temperature-dependent X-ray diffraction studies that each of the hexaphenoxy-substituted Pc derivatives has plural mesophases, and that the tetragonal columnar (Coltet) mesophase shows spontaneous perfect homeotropic alignment between two non-surface-treated glass plates without any defects and polydomain boundaries.

Synthesis and liquid crystal behavior of tris[2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] rare earth complexes

2007 ◽  
Vol 11 (02) ◽  
pp. 100-108 ◽  
Author(s):  
Ying Zhang ◽  
Weili Jiang ◽  
Jianzhuang Jiang ◽  
Qingbin Xue
Keyword(s):  
Rare Earth ◽  
Liquid Crystal ◽  
Liquid Crystalline ◽  
Optical Microscope ◽  
Rare Earth Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
Temperature Range ◽  
Ionic Size ◽  
Liquid Crystal Phase Transition

A series of tris[2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] rare earth(III) complexes M 2[ Pc ( OC 8 H 17)8]3 [ M = Eu , Gd , Y , Lu ] has been prepared by the reaction of corresponding bis[2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] rare earth complexes with M ( acac )3·n H 2 O in refluxing 1,2,4-trichlorobenzene. These liquid crystalline sandwich, triple-decker complexes were characterized by elemental analysis and various spectroscopic methods including 1 H NMR, UV-vis, IR and mass spectroscopies. Their liquid crystal phase transition behavior was studied by Polarized Optical Microscope, Differential Scanning Calorimeter and X-ray diffraction. The complexes, with octyloxy attached as side chains, showed rectangular columnar liquid crystal phases in a liquid crystal temperature range between 83 and 305°C. In addition to the rare earth contraction, both the transition temperature and the wide temperature range of the mesophase show a slight but obvious trend to decrease, respectively, in the same order. In contrast, the molecular packing of these complexes as revealed by X-ray diffraction was found to be almost independent of the ionic size of the central rare earth.

scholarly journals Discotic liquid crystals of transition metal complexes, 53†: synthesis and mesomorphism of phthalocyanines substituted by m-alkoxyphenylthio groups

2017 ◽  
Vol 21 (03) ◽  
pp. 159-178 ◽  
Author(s):  
Yoshiaki Chino ◽  
Kazuchika Ohta ◽  
Mutsumi Kimura ◽  
Mikio Yasutake
Keyword(s):  
Phase Transition ◽  
Transition Metal Complexes ◽  
Optical Microscope ◽  
Band Gaps ◽  
The Other ◽  
Discotic Liquid Crystals ◽  
Phase Transition Behavior ◽  
Temperature Dependent ◽  
X Ray ◽  
Optical Band Gaps

We have successfully synthesized a series of novel octakis([Formula: see text]-alkoxyphenylthio)phthalocyaninato copper(II) complexes, ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PcCu ([Formula: see text] = 2, 4, 6, 8, 10, 12, 14, 16: 1b~1i), by our developed method to reveal their mesomorphism. The phase transition behavior and mesophase structures have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. Interestingly, the very short chain-substituted derivatives, ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PcCu (1a) and ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PCu (1b), show a hexagonal ordered columnar (Col[Formula: see text] mesophase, whereas each of the other longer-chain-substituted derivatives, ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PcCu ([Formula: see text] = 4~16: 1c~1i), shows only rectangular ordered columnar (Col[Formula: see text] mesophase(s). In contrast to the present longer-chain-substituted phenylthio derivatives, each of the previous longer-chain-substituted phenoxy derivatives, ([Formula: see text]-C[Formula: see text]OPhO)[Formula: see text]PcCu ([Formula: see text] = 10–20), shows a different columnar mesophase of Col[Formula: see text]. We discuss this difference of mesomorphism from the viewpoint of the different steric hindrance originated by the peripheral substituents, PhO and PhS groups. Moreover, we could estimate the optical band gaps of ([Formula: see text]-C[Formula: see text]OPhO)[Formula: see text]PcCu and ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PcCu (1f) from absorption edge of the Q-bands to be 1.79 eV and 1.70 eV, respectively. Therefore, the phenylthio-substituted derivative gave a narrower band gap byca. 0.1 eV in comparison with the phenoxy-substituted derivative.

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