著者
Shiki Yagai
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.88, no.1, pp.28-58, 2015-01-15 (Released:2015-01-15)
参考文献数
164
被引用文献数
115

As details of exciting photonic and electronic properties arising from self-assembled functional dyes and related π-conjugated molecules become clearer, strategies for control of short and long-range chromophore–chromophore orientations, regulation of π–π stacking arrangements, construction of self-organized nano-to-microscale architectures, diversification of materials properties, analysis of self-assembly pathways, and impartment of stimuli-responsive properties, are all becoming important issues in the research area of organic functional materials. This article focuses on the supramolecular assemblies of dyes and related π-conjugated systems whose organization processes are rationally controlled by complementary multiple hydrogen bonding (CMHB) interactions between melamine and barbituric acid/cyanurate functional units. The article includes an overview of the construction principle of such systems, but special attention is focused on the work carried out in the authors’s group (since 2002) using azobenzene, diarylethene, merocyanine, perylene bisimide dyes, and π-conjugated oligomers including oligo(p-phenylenevinylene), oligo(p-phenyleneethynylene), and oligothiophenes. The design principles discussed in this account could open up new avenues to novel functional aspect and application of functional dyes and small-molecular π-conjugated systems.
著者
Makoto Yamashita
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
pp.20150355, (Released:2015-11-16)
被引用文献数
37

In this article, recent developments regarding the organometallic chemistry of boron-containing pincer ligands are reviewed. Boron-based pincer ligands can be subdivided into two main classes, which are based on either diazaborole or carborane. All the papers relevant to such boron-based pincer ligands that have been published since 2009 are included in this review, which also summarizes applications of transition metal complexes containing such boron-containing pincer ligands in catalytic and/or bond-cleavage reactions.
著者
Hiroaki Anbou Rui Umeda Yutaka Nishiyama
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.84, no.11, pp.1248-1250, 2011-11-15 (Released:2011-11-15)
参考文献数
28
被引用文献数
6

For the cesium carbonate-catalyzed α-phenylthiolation of carbonyl compounds with diphenyl disulfide, the yields of the α-phenylthio carbonyl compounds were dramatically improved by the addition of a catalytic amount of diphenyl diselenide.
著者
Arata Yajima
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.87, no.11, pp.1260-1264, 2014-11-15 (Released:2014-11-15)
参考文献数
34
被引用文献数
3

It is well known that there are nine stereoisomers of inositol that are composed of seven achiral compounds with a pair of enantiomers. However, there is no report regarding larger inositol homologs, contiguously substituted cycloalkane polyols; therefore, the numbers of stereoisomers of such compounds are unknown. This study provides a simple method to calculate the number of stereoisomers of inositol homologs with any carbon number. The established formulae may be useful in attracting novice students to the field of organic chemistry.
著者
Piotr Lulinski Lech Skulski
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.73, no.4, pp.951-956, 2000 (Released:2001-02-28)
参考文献数
46
被引用文献数
41 44

Five easy, relatively inexpensive, and environmentally-safe aromatic oxidative iodination procedures are presented; three of them are particularly suitable for deactivated arenes. Nine deactivated arenes, four halobenzenes, benzene, toluene, and N,N-dimethylaniline were reacted upon with the following anhydrous systems: diiodine/NaIO4 or (in four cases) NaIO3/acetic anhydride/glacial acetic acid, acidified with varying amounts of concd (98%) sulfuric acid; the following workups are explained. The aromatic oxidative iodination reactions proceeded mostly at room temperature and within 1—8 h to give fifteen mono- and two diiodinated purified products (sometimes obtained in 2—3 different ways) in 51—95% yields.
著者
Sasaki Yoh Yamase Toshihiro Ohashi Yuji Sasada Yoshio
出版者
The Chemical Society of Japan
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.60, no.12, pp.4285-4290, 1987
被引用文献数
27

The crystal structures of oxidized and photoreduced decatungstates are compared. Three specimens of decatungstate complexes were prepared in mixed solvents of H<SUB>2</SUB>O–CH<SUB>3</SUB>CN and were characterized by X-ray diffraction. Unit cell parameters are as follows: (C<SUB>6</SUB>H<SUB>16</SUB>N)<SUB>4</SUB>[W<SUB>10</SUB>O<SUB>32</SUB>]·2CH<SUB>3</SUB>CN; DECA <I>M<SUB>r</SUB></I>=2841.4, monoclinic, <I>P</I>2<SUB>1</SUB>⁄<I>n</I>, <I>a</I>=14.617(2), <I>b</I>=17.783(3), <I>c</I>=11.755(2) Å, β=100.27(2)°, <I>V</I>=3006.5(9) Å<SUP>3</SUP>, <I>Z</I>=2; (C<SUB>6</SUB>H<SUB>16</SUB>N)<SUB>4</SUB>[H<SUB>1.5</SUB>W<SUB>10</SUB>O<SUB>32</SUB>]·8H<SUB>2</SUB>O; RED1 <I>M<SUB>r</SUB></I>=2905.4, monoclinic, <I>P</I>2<SUB>1</SUB>⁄<I>n</I>, <I>a</I>=15.902(3), <I>b</I>=12.233(2), <I>c</I>=15.673(4) Å, β=93.76(2)°, <I>V</I>=3042(1), Å<SUP>3</SUP> <I>Z</I>=2; Na<SUB>4</SUB>[H<SUB>1.8</SUB>W<SUB>10</SUB>O<SUB>32</SUB>]·14H<SUB>2</SUB>O; RED2 <I>M<SUB>r</SUB></I>=2696.7, monoclinic, <I>C</I>2⁄<I>m</I>, <I>a</I>=16.123(5), <I>b</I>=12.636(3), <I>c</I>=12.168(4) Å, β=117.40(2)°, <I>V</I>=2202(1) Å<SUP>3</SUP>, <I>Z</I>=2; There is no obvious change in the anion frame among the three decatungstate complexes. Photoreduced decatungstates may coordinate protons which neutralize excess charge injected into anions. It is concluded that the structure of W<SUB>10</SUB>O<SUB>32</SUB> is not largely altered up to two-electron reduction.
著者
Shoichiro Yamada Ryutaro Tsuchida
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.33, no.1, pp.98-103, 1960 (Released:2006-04-12)
参考文献数
15
被引用文献数
23

The dichroism in the visible and ultraviolet region has been quantitatively determined at room temperature by Tsuchida and Kobayashi’s microscopic method with a single crystal of d, l-[Co en3] Cl3·3H2O, d, l- [Co en3] Br3·3H2O, d- [Co en3] Br3·2H2O and d, l-[Cr en3] Cl3·3H2O.It has been found that the [Co en3]3+ and the [Cr en3]3+ ion show a similar type of dichroism. For both the complex ions, the z-absorption is slightly stronger than the x-absorption in the wavelength region of the first absorption band and much weaker than the x-absorption in the region of the second absorption band.The results of the measurements are discussed in relation to the electronic state and the optical rotatory dispersion of the complex ions.
著者
Takayama Tomoaki Iwase Akihide Kudo Akihiko
出版者
The Chemical Society of Japan
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
2015
被引用文献数
28

Single-crystal KCaSrTa<sub>5</sub>O<sub>15</sub> nanorods were successfully synthesized by a polymerized complex method. SEM and TEM observations revealed that the nanorods growing along with the c-axis of the tungsten bronze structure possessed 40–100 nm of a diameter and 100–300 nm of a length. Tb(0.03 atom%)-doped KCaSrTa<sub>5</sub>O<sub>15</sub> nanorods gave a green luminescence due to the <sup>5</sup>D<sub>4</sub>→<sup>7</sup>F<sub>6</sub> and <sup>5</sup>D<sub>4</sub>→<sup>7</sup>F<sub>5</sub> transition of Tb<sup>3+</sup>, when the KCaSrTa<sub>5</sub>O<sub>15</sub> host was excited. The intensity of the luminescence was much higher than that by polycrystalline KCaSrTa<sub>5</sub>O<sub>15</sub> prepared by a solid-state reaction. This indicates that nonradiative deactivation at grain boundaries was suppressed in the KCaSrTa<sub>5</sub>O<sub>15</sub> nanorods compared to the polycrystalline KCaSrTa<sub>5</sub>O<sub>15</sub>. NiO cocatalyst-loaded KCaSrTa<sub>5</sub>O<sub>15</sub> nanorods split water into H<sub>2</sub> and O<sub>2</sub> with 6.6% of an apparent quantum yield at 254 nm. The efficiency was three times higher than that of the polycrystalline KCaSrTa<sub>5</sub>O<sub>15</sub>. The KCaSrTa<sub>5</sub>O<sub>15</sub> nanorods also showed photocatalytic activity for CO<sub>2</sub> reduction, when a Ag-cocatalyst was loaded. Stoichiometric amounts of CO and H<sub>2</sub> as reduction products and O<sub>2</sub> as an oxidation product were obtained. The activity for CO<sub>2</sub> reduction was improved by adding NaHCO<sub>3</sub> into the reactant solution, giving about 90% of a CO selectivity (CO/(CO+H<sub>2</sub>)).
著者
Shiina Isamu
出版者
The Chemical Society of Japan
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.87, no.2, pp.196-233, 2014
被引用文献数
28

After initially establishing a novel cyclization reaction of ω-hydroxycarboxylic acids (seco-acids) using 4-trifluoromethylbenzoic anhydride (TFBA) and Lewis acid catalysts to form the corresponding lactones, we discovered a more advanced method for this transformation using 2-methyl-6-nitrobenzoic anhydride (MNBA) as a coupling reagent with nucleophilic catalysts. The latter lactonization is promoted by acyl-transfer catalysts, such as 4-(dimethylamino)pyridine (DMAP), 4-pyrrolidinylpyridine (PPY), and 4-(dimethylamino)pyridine <i>N</i>-oxide (DMAPO). (+)-Ricinelaidic acid lactone ((+)-<b>2</b>) was first synthesized by the TFBA-mediated cyclization with Lewis acid catalysts, while the <i>threo</i>-aleuritic acid lactone (<b>20</b>) was alternatively synthesized by the MNBA-mediated cyclization with acyl-transfer catalysts. Using this effective lactonization technology to form the ester linkage under mild conditions, we then demonstrated the preparation of various large-, medium-, and small-sized natural and unnatural lactones including (−)-cephalosporolide D ((−)-<b>3</b>), (−)-octalactin A ((−)-<b>4</b>), (−)-octalactin B ((−)-<b>25</b>), 2-epibotcinolide (<b>49</b>), (−)- and (+)-2-hydroxytetracosanolides ((−)-<b>77</b> and (+)-<b>77</b>), (−)- and (+)-2-hydroxy-24-oxooctacosanolides ((−)-<b>78</b> and (+)-<b>78</b>), (−)-tetrahydrolipstatin ((−)-THL, (−)-<b>117</b>), and the erythromycin A skeletons <b>103b</b>, <b>103c</b>, <b>104c</b>, and <b>105b</b>. The transition structures involved in the formation of the β-lactones from the corresponding 3-hydroxycarboxylic acids were then determined using DFT calculations at the B3LYP/6-31G*//B3LYP/6-31G* level, and the reactivity of several seco-acids was successfully predicted on the basis of the calculated thermodynamic properties of the transition structures.
著者
Negishi Yuichi
出版者
The Chemical Society of Japan
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.87, no.3, pp.375-389, 2014
被引用文献数
37

Advances in developments in nanotechnology have encouraged the creation of highly functionalized nanomaterials. Thiolate-protected gold clusters (Au<i><sub>n</sub></i>(SR)<i><sub>m</sub></i>) less than 2 nm in size exhibit size-specific physical and chemical properties not observed in bulk metals. Therefore, they have attracted attention as functional units or building blocks in nanotechnology. The highly stable, magic Au<i><sub>n</sub></i>(SR)<i><sub>m</sub></i> clusters possess great potential as new nanomaterials. We are studying the following subjects related to magic Au<i><sub>n</sub></i>(SR)<i><sub>m</sub></i> clusters: (1) establishing methods to enhance their functionality, (2) developing high-resolution separation methods, and (3) utilizing the clusters as active sites in photocatalytic materials. Through these studies, we aim to create highly functional metal nanoclusters and apply them as highly active photocatalytic materials. The results of our efforts to date are summarized in this paper.
著者
Takahiro Kusukawa Genki Niwa Takato Sasaki Ryosuke Oosawa Wataru Himeno Masahiro Kato
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.86, no.3, pp.351-353, 2013-03-15 (Released:2013-03-15)
参考文献数
17
被引用文献数
8

The crystal structure analysis of glycerol was revisited and the hydrogen atoms of three hydroxy groups were observed. A hydrogen-bonded 3D network structure of glycerol was created by the formation of a wave-like sheet structure and its assembly through hydrogen bonding.
著者
Shiro Akabori Ko Ohno Kozo Narita
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.25, no.3, pp.214-218, 1952 (Released:2006-04-12)
参考文献数
13
被引用文献数
297

(1) A brief method for the characterization of carboxyl-terminal amino acids in peptides and proteins was investigated.(2) Several new amino acid hydrazides were synthesized.(3) Soveral di- and tri-peptides were hydrazinolyzed and identified their carboxylterminal amino acid.(4) The method was applied to beef insulin and tyrocidin for the demonstration of its applicability.
著者
Michiya Matsusaki
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.85, no.4, pp.401-414, 2012-04-15 (Released:2012-04-15)
参考文献数
53
被引用文献数
26

The creation of artificial three-dimensional (3D) tissues possessing structure and function similar to natural tissue is a key challenge for implantable tissues in tissue engineering, and for model tissues in pharmaceutical assays. This account is a summary of our current research toward this challenge. We have developed a simple and unique bottom-up approach, hierarchical cell manipulation technique, using nanometer-sized layer-by-layer films consisting of fibronectin and gelatin (FN–G) as a nano-extracellular matrix (nano-ECM). The FN–G nanofilms were prepared directly on the cell surface, and we discovered that at least 6 nm thick FN–G films acted as a stable adhesive surface for adhesion of the second cell layer. Various 3D-layered constructs consisting of single or multiple types of cells were successfully fabricated, and the higher cellular activities induced from the 3D-structures as compared to monolayer structure were observed. Furthermore, the multilayered constructs like a blood vessel wall structure indicated almost the same drug response as in vivo natural blood vessels, suggesting the possibility to use as an in vitro blood vessel model to analyze drug response. Recently, we also developed a rapid bottom-up approach by a single cell coating using FN–G nanofilms, because the fabrication of two-layers (2L) is limited through the above technique due to the time required for stable cell adhesion. This rapid approach easily provided approximately eight-layered (8L) 3D-tissues after only one day of incubation. The layer number, cell type, and location were all successfully controlled by altering the seeding cell number and order. Moreover, fully and homogeneously vascularized tissues of 1 cm width and 50 µm height were obtained by a sandwich culture of the endothelial cells. These hierarchical cell manipulations will be promising to achieve one of the dreams of biomedical field, in vitro creation of artificial 3D-tissue models.
著者
Ueda Joichi Kadowaki Kyoko
出版者
The Chemical Society of Japan
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.56, no.7, pp.1968-1971, 1983
被引用文献数
1

Procedures are described for the spectrophotometric determination of palladium and bismuth(III) with Semimethylxylenol Blue (SMXB). SMXB reacts with palladium and bismuth(III) to form reddish-violet 1:1 complexes. The optimum pH ranges for the color development are pH 1.0–1.7 for palladium and pH 1.0–1.4 for bismuth(III). The absorption maxima of the colored solutions lie at 565–568 nm and at 568–570 nm, respectively. Beer's law is obeyed over the range of 0.4–3.2 μg cm<SUP>−3</SUP> of palladium and 0.4–4.0 μg cm<SUP>−3</SUP> of bismuth(III), and the sensitivities of the determinations are 4.0×10<SUP>−3</SUP> μg Pd cm<SUP>−2</SUP> and 6.1×10<SUP>3</SUP> μg Bi cm<SUP>−2</SUP> for 0.001 of absorbance. For the palladium determination, gallium, tin(IV), bismuth(III), scandium, zirconium, and iron(III) interfere, but tin(IV), scandium, zirconium, and iron(III) can be masked by the addition of fluoride. For the bismuth(III) determination, gallium, tin(IV), scandium, zirconium, and iron(III) interfere, but the effect of iron(III) is eliminated by the addition of <small>L</small>-ascorbic acid, and tin(IV) and scandium can be masked by fluoride. A consecutive determination of palladium and bismuth(III) by the difference of the rates of color developments for their complexes was also studied.
著者
Muhammad Imran Abdullah Muhammad Ramzan Saeed Ashraf Janjua Muhammad Faizan Nazar Asif Mahmood
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
pp.20130146, (Released:2013-08-31)
被引用文献数
8 7

In the present study, ten metal free dyes for dye-sensitized solar cells (DSSCs) have been designed. These dyes have designed by structural modification of TC4. Density functional theory was used for structure optimization and determination of photo-physical properties. These dyes contain triphenylamine as electron-donor and cyanoacrylic acid as acceptor. Five π-spacers are used to connect the donor and acceptor. Two auxiliary donors are also used to assist the donor. Results of this study indicate that stronger electron-donating auxiliary groups and longer π-conjugation enhance, while electron-withdrawing fluorine at a π-spacer decreases the performance of dyes in DSSC. As compared to auxiliary electron-donors, π-spacers have a strong impact on the performance of the dyes in the DSSCs. Major absorption peaks of all dyes were in the visible region. These absorption peaks are associated with the π-π* transitions of the entire molecule. From calculations it is clear that all dyes will be good photosensitizers in DSSC. The present calculations will provide new ways for experimentalists to synthesize high-performance dyes.
著者
Tomoki Nishimura Takeshi Cho Andrew M. Kelley Magdalena E. Powell John S. Fossey Steven D. Bull Tony D. James Hiroyasu Masunaga Isamu Akiba Kazuo Sakurai
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
pp.1008170144-1008170144, (Released:2010-08-21)
参考文献数
42
被引用文献数
9

Synthetic DNA-transfection reagents can overcome safety issues raised by use of viral DNA vectors. One of these candidates is a cationic lipid that can form a supramolecular complex with DNA. We have been working in a series of aromatic diamine lipids with different tail length from C6 to C18: [N-(3,5-dialkylbenzyl)ethane-1,2-diamine, denoted DA] as such a lipid. The present paper describes the synthesis and the fundamental properties of DA. SAXS from DA solution showed bilayer vesicle formation, while it showed lamellar formation after the complexation with DNA. When we measured the N/P ratio (molar ratio of the amine groups (N) in DA to phosphate groups (P) in the DNA) dependence of SAXS, the lamellar peak (spacing = 5.0 nm) increased proportionally to the added DNA concentration at N/P ≥ 8. On the other hand, in the range of N/P < 8, the spacing was increased to 5.5 nm and the area decreased as DNA increased. These different features between N/P ≥ 8 and N/P < 8 suggest that the lamellar supramolecular structures differ according to the composition.
著者
Mahgoub Safaa Abd El-Salam Fahmy Atiat Mohammed Aly Morsy Mohammed Badr Mahmoud Zaif Amin
出版者
The Chemical Society of Japan
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.59, no.5, pp.1605-1606, 1986
被引用文献数
5

Thermolysis of acetophenone phenylhydrazone by reflux in air for 24 h gives ammonia, benzonitrile, acetophenone, biphenyl, aniline, <I>o</I>- and <I>p</I>-toluidines, together with 7-methyl-3-phenylindole, while that of benzophenone phenylhydrazone gives ammonia, benzophenone, <I>N</I>-benzhydrylideneaniline, biphenyl, aniline, benzonitrile, and 9-phenylacridine.
著者
Handa Makoto Matsumoto Hiroki Yoshioka Daisuke NUKADA Ryoji MIKURIYA Masahiro HIROMITSU Ichiro KASUGA Kuninobu
出版者
公益社団法人 日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.71, no.8, pp.1811-1816, 1998-08-15
参考文献数
49
被引用文献数
10

A series of chain complexes of molybdenum(II) trifluoroacetate linked by <i>p</i>-quinones, [Mo<sub>2</sub>(O<sub>2</sub>CCF<sub>3</sub>)<sub>4</sub>(<i>p</i>-quin)]<sub><i>n</i></sub>, <i>p</i>-quin = 9,10-anthraquinone (9,10-aq), 2,6-dimethyl-1,4-benzoquinone (2,6-dmbq), and 1,4-naphthoquinone (1,4-nq) have been prepared. The X-ray structure analyses showed that the carbonyl oxygens of the <i>p</i>-quinones are coordinated to the Mo<sub>2</sub> dimers with distances of 2.478(6) and 2.532(5) &Aring; (for 9,10-aq), 2.619(9) and 2.596(10) &Aring; (for 2,6-dmbq), and 2.522(8) &Aring; (for 1,4-nq), respectively. The Mo&ndash;Mo bond distances are 2.107(1)&mdash;2.117(1) &Aring;, which are slightly longer than that of Mo<sub>2</sub>(O<sub>2</sub>CCF<sub>3</sub>)<sub>4</sub> (2.090(4) &Aring;). Elongation of the C=O and C=C bonds of the 9,10-aq and 2,6-dmbq molecules on the coordination has been observed, but the bond distances of the coordinated and uncoordinated 1,4-nq molecules are similar to each other. The difference is discussed in terms of the oxidizing abilities and the symmetries of the <i>p</i>-quinones.
著者
Yasuyuki Takeda Koji Katsuta Yoshihisa Inoue Tadao Hakushi
出版者
The Chemical Society of Japan
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.61, no.3, pp.627-632, 1988 (Released:2006-06-27)
参考文献数
41
被引用文献数
37

Conductivities of alkali metal salts in the presence of 15-crown-5 (15C5), 16-crown-5 (16C5), and benzo-15-crown-5 (B15C5) were measured at 25 °C in acetonitrile, propylene carbonate, and methanol. Formation constants (KML+) of 1:1 complexes of 15C5 and 16C5 with alkali metal ions and conductance parameters (λ0 and å) of the Na+ complexes of 15C5, 16C5, and B15C5 were determined, λ0 and å being limiting ionic molar conductivity and distance of closest approach of ions, respectively. In general, selectivities of 15C5 and 16C5 for alkali metal ions show the size-fit correlation. In contrast to 15C5, 16C5 forms much the most stable complex with Na+ in every solvent. Generally, KML+-value sequences of a given crown ether complex for the solvents are the reverse of donor-number sequences of the solvents. Value of å increases with an increase in the cationic size (Na+→Na(15C5)+→Na(16C5)+→Na(B15C5)+). Mobility of the Na+–crown ether complex decreases with an increase in the size of the crown ether. From λ0 values and Walden products of these Na(crown ether)+ complexes and a tetrapropylammonium ion, it seems likely that Na(15C5)+ and Na(16C5)+ act as structure breakers in hydrogen-bonding solvents, whereas Na(B15C5)+ as a structure maker.
著者
Himeno Sadayuki Hori Toshitaka Saito Atsuyoshi
出版者
公益社団法人 日本化学会
雑誌
Bulletin of the Chemical Society of Japan
巻号頁・発行日
vol.62, no.7, pp.2184-2188, 1989
被引用文献数
35

The formation conditions of a yellow Dawson-type S<SUB>2</SUB>Mo<SUB>18</SUB>O<SUB>62</SUB><SUP>4&minus;</SUP> anion have been investigated as functions of the concentrations of Mo(VI), H<SUB>2</SUB>SO<SUB>4</SUB>, organic solvents, the nature of the organic solvents used, temperature of the solution, and the reaction time. For a 50 mM Mo(VI)/50% (v/v) acetonitrile system, the yellow S<SUB>2</SUB>Mo<SUB>18</SUB>O<SUB>62</SUB><SUP>4&minus;</SUP> anion formed in 0.2&ndash;1.0 M H<SUB>2</SUB>SO<SUB>4</SUB>, while a pale-yellow Mo<SUB>6</SUB>O<SUB>19</SUB><SUP>2&minus;</SUP> anion did in 0.04&ndash;0.3 M H<SUB>2</SUB>SO<SUB>4</SUB>. The yellow heteropolyanion is electrochemically reduced in six successive steps to mixed-valence heteropoly blues at the glassy carbon electrode. Each of the first four waves corresponds to a reversible two-electron transfer. The mixed-valence blue species were characterized by their inherent visible and infrared (IR) spectra.