A Novel Series of Heteropolynuclear Metallomesogens: Organopalladium Complexes with Ferrocenophane-Containing Ligands

Kadkin, Oleg N.,An, Jaein,Han, Haksoo,Galyametdinov, Yuri G. WILEY-VCH Verlag 2008 European journal of inorganic chemistry Vol.2008 No.10

<P>Ferrocenophane-containing (Fcph) Schiff's bases p-C<SUB>12</SUB>H<SUB>25</SUB>O(C<SUB>6</SUB>H<SUB>4</SUB>)CH=N(C<SUB>6</SUB>H<SUB>4</SUB>)Fcph (L<SUP>A</SUP>H) and p-C<SUB>12</SUB>H<SUB>25</SUB>O(C<SUB>6</SUB>H<SUB>4</SUB>)COO(C<SUB>6</SUB>H<SUB>4</SUB>)CH=N(C<SUB>6</SUB>H<SUB>4</SUB>)Fcph (L<SUP>B</SUP>H) react with palladium(II) acetate to form μ-acetato- and chloro-bridged dimeric organopalladium complexes. By exchanging acetato-groups with the chloride anions, μ-chloro-bridged heteropolynuclear dimers are obtained that show thermotropic smectic A phases over a temperature range of 198 to 260 °C. The complexes [PdClL<SUP>A</SUP>]<SUB>2</SUB> and [PdClL<SUP>B</SUP>]<SUB>2</SUB> can be transformed into a variety of mixed-ligand Pd<SUP>II</SUP> complexes by treatment with salicylaldimine p-C<SUB>12</SUB>H<SUB>25</SUB>O(C<SUB>6</SUB>H<SUB>4</SUB>)COO(C<SUB>6</SUB>H<SUB>3</SUB>)(OH)CH=N(C<SUB>6</SUB>H<SUB>4</SUB>)Fcph (L<SUP>C</SUP>H) and β-aminovinyl ketone p-C<SUB>12</SUB>H<SUB>25</SUB>O(C<SUB>6</SUB>H<SUB>4</SUB>)COCH=CHNH(C<SUB>6</SUB>H<SUB>4</SUB>)Fcph (L<SUP>D</SUP>H). The obtained mixed-ligand heterometallic complexes [PdL<SUP>A</SUP>L<SUP>C</SUP>], [PdL<SUP>B</SUP>L<SUP>C</SUP>], [PdL<SUP>A</SUP>L<SUP>D</SUP>] and [PdL<SUP>B</SUP>L<SUP>D</SUP>] exhibit enantiotropic, thermotropic nematic phases over a broad temperature range from 71 to 205 °C. The structures of the synthesized compounds were characterized by means of <SUP>1</SUP>H NMR, IR and UV spectroscopy, as well as elemental analysis. The liquid crystalline properties were studied by polarising optical microscopy and DSC. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</P> <B>Graphic Abstract</B> <P>Liquid crystalline heteropolynuclear complexes based on palladium(II) chelates withvarious ferrocenophane-containing ligands were synthesized. <img src='wiley_img/14341948-2008-2008-10-EJIC200700750-fig000.gif' alt='wiley_img/14341948-2008-2008-10-EJIC200700750-fig000'> </P>

Glycerol as Ligand: The Synthesis, Crystal Structure, and Properties of Compounds [Ln₂(H₂L)₂(H₃L)₄][Re₆Q₈(CN)₆], Ln = La, Nd, Gd, Q = S, Se

Naumov, Nikolai G.,Tarasenko, Maria S.,Virovets, Alexander V.,Kim, Youngmee,Kim, Sung-Jin,Fedorov, Vladimir E. Wiley-VCH 2006 European journal of inorganic chemistry Vol. No.

<P>The interaction of aqueous solutions of octahedral cluster anions [Re<SUB>6</SUB>Q<SUB>8</SUB>(CN)<SUB>6</SUB>]<SUP>4–</SUP> with rare earth cations in the presence of glycerol resulted in the formation of a new family of compounds [Ln<SUB>2</SUB>(H<SUB>2</SUB>L)<SUB>2</SUB>(H<SUB>3</SUB>L)<SUB>4</SUB>][Re<SUB>6</SUB>Q<SUB>8</SUB>(CN)<SUB>6</SUB>] (where Ln = La, Nd, and Gd; Q = S, Se; H<SUB>3</SUB>L = glycerol; H<SUB>2</SUB>L<SUP>–</SUP> = glycerolate anion). All compounds are isostructural and crystallize in the P<TEX>$\bar {1}$</TEX> space group. Crystal structures are built from octahedral cluster anions [Re<SUB>6</SUB>Q<SUB>8</SUB>(CN)<SUB>6</SUB>]<SUP>4–</SUP> and centrosymmetrical dimers [Ln<SUB>2</SUB>(H<SUB>2</SUB>L)<SUB>2</SUB>(H<SUB>3</SUB>L)<SUB>4</SUB>]<SUP>4+</SUP> that have three different binding modes of glycerol. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2006-2006-2-EJIC200500542-fig000.gif' alt='wiley_img/14341948-2006-2006-2-EJIC200500542-fig000'> </P>

Synthesis of the Tetraketide Lactones from the Pikromycin Biosynthetic Pathway

Oh, Hong-Se,Yun, Ji-Suk,Nah, Ki-Hyun,Kang, Han-Young,Sherman, David H. WILEY-VCH Verlag 2007 European journal of organic chemistry Vol.2007 No.20

<P>Synthesis of tetraketide lactones 2 and 3, which are likely to be produced by a model pikromycin polyketide synthase (PKS), has been investigated. The tetraketide lactones with six-membered rings, 2a and 2b, were synthesized successfully by the asymmetric aldol reaction, allylation, and the Reformatsky reaction. The attempted synthesis of tetraketide lactones with eight-membered rings, 3a and 3b, led to the formation of the compounds 2a and 2b. The synthesis of another tetraketide lactone compounds 35 was attempted with the hope that introducing an additional methyl group would lead to a change in thermodynamic stability. However, it produced the corresponding tetraketide lactone 34 with a six-membered ring. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/1434193X-2007-2007-20-EJOC200700254-fig000.gif' alt='wiley_img/1434193X-2007-2007-20-EJOC200700254-fig000'> </P>

Large-Scale Synthesis of Water Dispersible Ceria Nanocrystals by a Simple Sol–Gel Process and Their Use as a Chemical Mechanical Planarization Slurry

Yu, Taekyung,Park, Yong Il,Kang, Min-Cheol,Joo, Jin,Park, Jin Kyung,Won, Ho Youn,Kim, Jae Jeong,Hyeon, Taeghwan WILEY-VCH Verlag 2008 European journal of inorganic chemistry Vol.2008 No.6

<P>Ceria nanocrystals with a cube shape were synthesized from the hydrolytic sol–gel reaction of cerium salt in the presence of oleylamine. The overall synthetic process is very simple and readily applicable to the large-scale synthesis of tens of grams of product in a single reaction in air. These ceria nanocrystals are readily dispersible in aqueous media without the addition of any extra dispersing agent. The aqueous dispersion of the ceria nanocrystals was successfully used as a chemical mechanical polishing slurry, and it exhibited high removal selectivity between silicon oxide and silicon nitride at pH 7.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2008-2008-6-EJIC200700979-fig000.gif' alt='wiley_img/14341948-2008-2008-6-EJIC200700979-fig000'> </P>

A Practical Gold-Catalyzed Route to 4-Substituted Oxazolidin-2-ones from N-Boc Propargylamines

Lee, Eun-Sun,Yeom, Hyun-Suk,Hwang, Ji-Hyun,Shin, Seunghoon WILEY-VCH Verlag 2007 EUROPEAN JOURNAL OF ORGANIC CHEMISTRY Vol.2007 No.21

<P>Au<SUP>I</SUP>-catalyzed cyclization of N-Boc propargylamines into 4-alkylidene oxazolidin-2-ones is described. This modularapproach provides access to a variety of nonproteogenic 4-substituted oxazolidinones that are important in asymmetric synthesis and biological applications. The current flexible route is characterized by low catalyst loading, mild conditions, and operational simplicity.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/1434193X-2007-2007-21-EJOC200700210-fig000.gif' alt='wiley_img/1434193X-2007-2007-21-EJOC200700210-fig000'> </P>

A Poly(bicyclic dimer) and a Cyclic Tetramer: Ligand Isomerism of S₂O₂ Macrocycles During the Assembly of Supramolecular Silver(I) Complexes

Lee, So Young,Seo, Joobeom,Yoon, Il,Kim, Chung-Sik,Choi, Kyu Seong,Kim, Jae Sang,Lee, Shim Sung WILEY-VCH Verlag 2006 European journal of inorganic chemistry Vol.2006 No.17

<P>Two isomeric S<SUB>2</SUB>O<SUB>2</SUB> macrocycles (L<SUP>1</SUP> and L<SUP>2</SUP>) with a 14-membered cavity have been synthesised as a model system with different binding modes. Self-assembly reactions of L<SUP>1</SUP> and L<SUP>2</SUP> with silver perchlorate afford the respective ligand-directed cyclic oligomer complexes with different shapes: a poly(bicyclic dimer) (1) and a discrete cyclic tetramer (2). The formation of these supramolecular complexes is discussed in terms of conformational discrimination of two isomeric macrocycles due to ring rigidity and interdonor distances.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2006-2006-17-EJIC200600290-fig000.gif' alt='wiley_img/14341948-2006-2006-17-EJIC200600290-fig000'> </P>

[Cu^II₄] Clusters From the Self-Assembly of Two Imidazolidinyl 2-Phenolate-Bridged [Cu^II₂] Units: The Role of the Chloride Bridge

Paital, Alok Ranjan,Hong, Chang Seop,Kim, Hyoung Chan,Ray, Debashis WILEY-VCH Verlag 2007 European journal of inorganic chemistry Vol.2007 No.12

<P>A new family of tetracopper clusters [Cu<SUB>4</SUB>(μ<SUB>4</SUB>-X)L<SUB>2</SUB>]ClO<SUB>4</SUB>·nH<SUB>2</SUB>O (1a–c) [X = Cl, Br, I; n = 12, 2, 2; H<SUB>3</SUB>L = 2-(2′-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine] have been synthesised and characterised. The X-ray crystal structure of 1a reveals that the template action of the spherical Cl<SUP>–</SUP> anion (μ<SUB>4</SUB>-Cl<SUP>–</SUP>), which features a unique rectangular planar bridging mode, is responsible for the self-assembly of two [Cu<SUB>2</SUB>L]<SUP>+</SUP> units in complex 1a. In this family of complexes the spherical halides serve as templates to assemble the dimeric unit into tetrameric complexes, which gives an insight into the role of the halide bridge in tetranuclear complex formation. The capacity of this bridge to mediate magnetic coupling has been examined by bulk magnetic measurements for complex 1a. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2007-2007-12-EJIC200600917-fig000.gif' alt='wiley_img/14341948-2007-2007-12-EJIC200600917-fig000'> </P>

Mesolamellar Phases Containing [Re₆Q₈(CN)₆]^4– (Q = Te, Se, S) Cluster Anions

Suh, Min-Jung,Vien, Vo,Huh, Seong,Kim, Youngmee,Kim, Sung-Jin WILEY-VCH Verlag 2008 European journal of inorganic chemistry Vol.2008 No.5

<P>We synthesized new mesostructured materials through the surfactant-templated assembly of octahedral rhenium cluster [Re<SUB>6</SUB>Q<SUB>8</SUB>(CN)<SUB>6</SUB>]<SUP>4–</SUP> (Q = Te, Se and S) anions. The mesostructured lamellar phases with the general formula [C<SUB>n</SUB>H<SUB>2n+1</SUB>N(CH<SUB>3</SUB>)<SUB>3</SUB>]<SUB>4</SUB>[Re<SUB>6</SUB>Q<SUB>8</SUB>(CN)<SUB>6</SUB>] (n = 14, 16, 18; Q = Te, Se, S; 1: n = 14, Q = Te; 2: n = 16, Q = Te; 3: n = 18, Q = Te; 4: n = 16, Q = Se; 5: n = 16, Q = S) were prepared by an ion exchange/precipitation reaction of alkyltrimethylammonium surfactants and the corresponding cluster K<SUB>4</SUB>[Re<SUB>6</SUB>Q<SUB>8</SUB>(CN)<SUB>6</SUB>] in an H<SUB>2</SUB>O/acetone medium at room temperature. The orange plate-like crystals of 1 and 4 were obtained by slow concentration of their solutions and their crystal structures determined by single-crystal X-ray diffraction. In the structure, the rhenium clusters form layers with a pseudo-hexagonal arrangement, and these inorganic layers are separated by a bilayer of interdigitated surfactant cations. Compounds 1–5 were characterized using powder X-ray diffraction, TEM, IR, Raman, FL, UV/Vis spectroscopy, and thermogravimetric analysis.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2008-2008-5-EJIC200701125-fig000.gif' alt='wiley_img/14341948-2008-2008-5-EJIC200701125-fig000'> </P>

Submicrosticks versus Submicrohelices by Sonication – Assembly of PdCl₂ Nanoparticles on Those Morphologies

Noh, Tae Hwan,Kim, Shin A,Lee, Su Yeon,Jung, Ok-Sang WILEY-VCH Verlag 2009 European journal of inorganic chemistry Vol.2009 No.29

<P>An unprecedented modulation of submicrohelix versus submicrostick morphologies by sonication has been systematically carried out on new propeller-type tri-O-isonicotinoylphloroglucinol. The formation and control of uniform submicrohelix and submicrostick morphologies show subtle external sonication media effects. The first control of submicrohelices versus submicrosticks by sonication without any additive or template seems to be a function of conformational isomers. The facile loading of PdCl<SUB>2</SUB> nanoparticles from K<SUB>2</SUB>PdCl<SUB>4</SUB> on the morphologies is a conceptually advanced method of nanoparticle–submicromorphology interaction.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>For tri-O-isonicotinoylphloroglucinol, the formation and control of uniform helix and stick morphologies shows subtle external sonication media effects. The first control of submicrohelices versus submicrosticks by sonication without any additives seems to be a function of conformational isomers. The present approach to loading PdCl<SUB>2</SUB> nanoparticles from K<SUB>2</SUB>PdCl<SUB>4</SUB> on the morphologies is a conceptually advanced method of metal-surface–donor interaction. <img src='wiley_img/14341948-2009-2009-29-30-EJIC200900698-fig000.gif' alt='wiley_img/14341948-2009-2009-29-30-EJIC200900698-fig000'> </P>

Synthesis and Aqueous Colloidal Solutions of RE₂(OH)₅NO₃·nH₂O (RE = Nd and La)

Lee, Kyung-Hee,Byeon, Song-Ho WILEY-VCH Verlag 2009 European journal of inorganic chemistry Vol.2009 No.31

<P>A new, simple route leading to layered rare-earth hydroxy nitrates was developed. The pH-independent procedure uses ethanol containing alkali-metal hydroxide (KOH, RbOH, or CsOH) as a solvothermal medium. Two new, layered rare-earth hydroxy nitrates (LRHs), Nd<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O and La<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O, were prepared by this nonaqueous solvothermal reaction. Because the RE = Nd and La members have not yet been synthesized in an aqueous system, the successful synthesis of these compounds implies the completion of the RE<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O (RE = rare earths) series. The typical properties of a layered structure was demonstrated by ready ion-exchange reactions between NO<SUB>3</SUB><SUP>–</SUP> and some organic anions such as decanoate, decanesulfonate, and decyl sulfate. In particular, the as-synthesized hydroxide from solvothermal reaction, where the alkali-metal nitrates are partially intercalated in the interlayer gallery, form an aqueous colloidal solution under ultrasonic treatment. Hydration of the LRHs intercalated with alkali-metal salts results in the formation of colloidal LRH suspensions in water. The colloidal character of the LRH solutions is supported by the Tyndall effect, TEM, and AFM images.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>A new, simple route was developed to synthesize the complete rare-earth series of the RE<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O family. The hydration of La<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O and Nd<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O synthesized by this nonaqueous solvothermal method yielded transparent aqueous colloidal solutions. <img src='wiley_img/14341948-2009-2009-31-EJIC200900635-fig000.gif' alt='wiley_img/14341948-2009-2009-31-EJIC200900635-fig000'> </P>