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Mironov, Yuri V.,Brylev, Konstantin A.,Kim, Sung-Jin,Kozlova, Svetlana G.,Kitamura, Noboru,Fedorov, Vladimir E. Elsevier 2011 Inorganica chimica acta Vol.370 No.1
<P><B>Graphical abstract</B></P><P>New hexarhenium cyanohydroxo cluster anion [Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]<SUP>4−</SUP> was synthesized and crystallized as a salt of the composition Cs<SUB>2.75</SUB>K<SUB>1.25</SUB>[Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]·H<SUB>2</SUB>O (<B>1</B>). Based on this anion two other compounds, namely [Cu(NH<SUB>3</SUB>)<SUB>5</SUB>]<SUB>2</SUB>[Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]·8H<SUB>2</SUB>O and [{Cu(CH<SUB>3</SUB>NH<SUB>2</SUB>)<SUB>4</SUB>}<SUB>2</SUB>Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>] were synthesized. All of these three compounds were characterized by a single-crystal X-ray diffraction method. The luminescence properties of <B>1</B> were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]<SUP>4−</SUP> was elucidated by DFT calculations.<ce:figure id='f0005'></ce:figure></P><P><B>Research highlights</B></P><P>► The partial substitution of terminal OH ligands in Re<SUB>6</SUB> cluster complex leads to <I>trans</I>-[Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]<SUP>4−</SUP>. ► The complex synthesized is a new multifunctional building block. ► The compound emits above 600nm in both solid phase and an aqueous solution.</P> <P><B>Abstract</B></P><P>A hexarhenium cyanohydroxo anionic cluster complex [Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]<SUP>4−</SUP> was synthesized for the first time starting from [Re<SUB>6</SUB>Se<SUB>8</SUB>(OH)<SUB>6</SUB>]<SUP>4−</SUP>, which was crystallized as a salt of the composition Cs<SUB>2.75</SUB>K<SUB>1.25</SUB>[Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]·H<SUB>2</SUB>O (<B>1</B>). The reaction of the complex with Cu<SUP>2+</SUP> in an aqueous ammonia or methylamine solutions afforded [Cu(NH<SUB>3</SUB>)<SUB>5</SUB>]<SUB>2</SUB>[Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]·8H<SUB>2</SUB>O (<B>2</B>) or [{Cu(CH<SUB>3</SUB>NH<SUB>2</SUB>)<SUB>4</SUB>}<SUB>2</SUB>Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>] (<B>3</B>), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound <B>1</B> is crystallized in the tetragonal space group <I>I</I>4<I>/m</I> with eight formula units per cell (<I>a</I>=<I>b</I>=17.4823(14)Å, <I>c</I>=19.430(2)Å, <I>V</I>=5938.3(10)Å<SUP>3</SUP>); compound <B>2</B> is crystallized in the monoclinic space group <I>P</I>2<SUB>1</SUB><I>/n</I> with two formula units per cell (<I>a</I>=12.1845(13)Å, <I>b</I>=8.6554(9)Å, <I>c</I>=19.2568(19)Å, <I>β</I>=91.081(2)°, <I>V</I>=2030.5(4)Å<SUP>3</SUP>); compound <B>3</B> is crystallized in the orthorhombic space group <I>Cmcm</I> with four formula units per cell (<I>a</I>=19.816(4)Å, <I>b</I>=14.611(3)Å, <I>c</I>=13.751(3)Å, <I>V</I>=3981.2(13)Å<SUP>3</SUP>). The luminescence properties of <B>1</B> were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re<SUB>6</SUB>Se<SUB>8</SUB>(CN)<SUB>4</SUB>(OH)<SUB>2</SUB>]<SUP>4−</SUP> was elucidated by DFT calculations.</P>
Mironov, Yuri V.,Naumov, Nikolai G.,Kozlova, Svetlana G.,Kim, Sung-Jin,Fedorov, Vladimir E. WILEY-VCH Verlag 2005 Angewandte Chemie Vol.117 No.42
<B>Graphic Abstract</B> <P>Die Cyanidcluster [Re<SUB>12</SUB>CS<SUB>17</SUB>(CN)<SUB>6</SUB>]<SUP>n−</SUP> (n=8 oder 6) könnten als Bausteine für polymere Materialien dienen. Sie entstehen aus ReS<SUB>2</SUB> in geschmolzenem KCN bei 750 °C. Die Clustereinheit umfasst zwei {Re<SUB>6</SUB>}-Oktaeder, die durch drei μ<SUB>2</SUB>-S-Brücken und ein interstitielles μ<SUB>6</SUB>-C-Atom verbunden sind (siehe Bild). <img src='wiley_img/00448249-2005-117-42-ANGE200501911-content.gif' alt='wiley_img/00448249-2005-117-42-ANGE200501911-content'> </P>
Yarovoi, Spartak S.,Mironov, Yuri V.,Naumov, Dmitry Y.,Gatilov, Yuri V.,Kozlova, Svetlana G.,Kim, Sung-Jin,Fedorov, Vladimir E. WILEY-VCH Verlag 2005 European journal of inorganic chemistry Vol.2005 No.19
<P>Two novel rhenium cluster compounds, K<SUB>4</SUB>[Re<SUB>6</SUB>S<SUB>8</SUB>(OH)<SUB>6</SUB>]·8H<SUB>2</SUB>O (1) and K<SUB>4</SUB>[Re<SUB>6</SUB>Se<SUB>8</SUB>(OH)<SUB>6</SUB>]·8H<SUB>2</SUB>O (2), containing octahedral cluster chalcogenide anionic complexes [Re<SUB>6</SUB>Q<SUB>8</SUB>(OH)<SUB>6</SUB>]<SUP>4–</SUP> with terminal hydroxo ligands have been synthesized by the reaction of Re<SUB>6</SUB>Q<SUB>8</SUB>Br<SUB>2</SUB> (Q = S, Se) with molten KOH. Two chalcohalide compounds, one known (Cs<SUB>4</SUB>[Re<SUB>6</SUB>S<SUB>8</SUB>Br<SUB>6</SUB>]·2H<SUB>2</SUB>O, 3) and another new (Cs<SUB>3</SUB>[Re<SUB>6</SUB>Se<SUB>8</SUB>Cl<SUB>6</SUB>]·2H<SUB>2</SUB>O, 4), were prepared by reactions of 1 and 2 with CsX and HX (X = Br, Cl) in an aqueous solution. Compounds 1, 2, and 4 have been characterized by the single-crystal X-ray diffraction method. Compounds 1 and 2 are crystallized in triclinic space group P<TEX>$\bar {1}$</TEX> with one formula unit in the cell of dimensions a = 8.4936(8) Å, b = 8.9101(11) Å, c = 10.5940(13) Å, α = 77.935(11)°, β = 75.933(9)°, γ = 71.244(10)°, V = 728.9(1) Å<SUP>3</SUP> (compound 1) and a = 8.613(1) Å, b = 8.996(1) Å, c = 10.057(1) Å, α = 78.587(2)°, β = 77.811(2)°, γ = 71.728(2)°, V = 715.9(2) Å<SUP>3</SUP> (compound 2). Compound 4 crystallizes in the monoclinic space group P2<SUB>1</SUB>/n with two formula units in the cell of dimensions a = 9.819(3) Å, b = 12.925(4) Å, c = 11.756(4) Å, β = 113.38(3)°, V = 1369.6(8) Å<SUP>3</SUP>. Compounds 1 and 2 display luminescent properties. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2005-2005-19-EJIC200500284-fig000.gif' alt='wiley_img/14341948-2005-2005-19-EJIC200500284-fig000'> </P>
Brylev, Konstantin A.,Mironov, Yuri V.,Fedorov, Vladimir E.,Kim, Sung-Jin,Pietzsch, Hans-Jü,rgen,Stephan, Holger,Ito, Akitaka,Kitamura, Noboru Elsevier 2010 Inorganica chimica acta Vol.363 No.11
<P><B>Graphical abstract</B></P><P>A new hexanuclear anionic rhenium cluster complex [Re<SUB>6</SUB>S<SUB>8</SUB>(CH<SUB>3</SUB>COO)<SUB>6</SUB>]<SUP>4–</SUP> have been synthesized and characterized by X-ray single-crystal diffraction analysis, IR, <SUP>1</SUP>H NMR, UV/vis, and luminescence spectroscopies. The complex is the first demonstration of any chalcogenide hexanuclear clusters coordinated with acetic acid anions.</P><ce:figure></ce:figure> <P><B>Abstract</B></P><P>A room-temperature reaction between [Re<SUB>6</SUB>S<SUB>8</SUB>(OH)<SUB>6</SUB>]<SUP>4−</SUP> and acetic acid in an aqueous solution resulted in the substitution of all terminal hydroxo groups by acetate ligands, affording a new hexanuclear anionic rhenium cluster complex [Re<SUB>6</SUB>S<SUB>8</SUB>(CH<SUB>3</SUB>COO)<SUB>6</SUB>]<SUP>4−</SUP>. The complex was isolated as a potassium salt with the composition of K<SUB>4</SUB>[Re<SUB>6</SUB>S<SUB>8</SUB>(CH<SUB>3</SUB>COO)<SUB>6</SUB>]·8H<SUB>2</SUB>O (<B>1</B>) and characterized by X-ray single-crystal diffraction and elemental analyses, IR, <SUP>1</SUP>H NMR, UV–Vis, and luminescence spectroscopies.</P>