Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, B.C., V5A 1S6, Canada.
Dalton Trans. 2013 Nov 14;42(42):14982-91. doi: 10.1039/c3dt50974e. Epub 2013 Aug 12.
A series of ammonium and tetraalkylammonium metal isothiocyanate salts of the type Q(y)[M(NCS)x] (M = Cr(III), x = 6, y = 3, Q = NH4(+), Me4N(+), Et4N(+), n-Bu4N(+); M = Mn(II), x = 6, y = 4, Q = Me4N(+); M = Mn(II), x = 5, y = 3, Q = Et4N(+); M = Fe(III), x = 6, y = 3, Q = Me4N(+), Et4N(+), n-Bu4N(+); M = Co(II), x = 4, y = 2, Q = n-Bu4N(+); M = Eu(III), Gd(III), Dy(III), x = 6, y = 3, Q = Bu4N(+)) has been synthesized and structurally characterized. The octahedral Cr(III) salts are isostructural to previously and newly reported Fe(III) salts. The Ln(III)-containing anions are also octahedral. For Mn(II), although the Me4N(+) salt is octahedral, the Et4N(+) salt Mn(NCS)5 possesses a distorted trigonal bipyramidal geometry. For (Et4N)3[Fe(NCS)6] and (n-Bu4N)3[Fe(NCS)6], a solid-state size-dependent change in colour from red to green was observed and was attributed to a light scattering phenomenon in the crystalline samples.
已合成并结构表征了一系列类型为 Q(y)[M(NCS)x] 的铵和四烷基铵金属异硫氰酸盐盐（M = Cr(III)，x = 6，y = 3，Q = NH4(+)，Me4N(+)，Et4N(+)，n-Bu4N(+)；M = Mn(II)，x = 6，y = 4，Q = Me4N(+)；M = Mn(II)，x = 5，y = 3，Q = Et4N(+)；M = Fe(III)，x = 6，y = 3，Q = Me4N(+)，Et4N(+)，n-Bu4N(+)；M = Co(II)，x = 4，y = 2，Q = n-Bu4N(+)；M = Eu(III)，Gd(III)，Dy(III)，x = 6，y = 3，Q = Bu4N(+)）。八面体 Cr(III)盐与先前和新报道的 Fe(III)盐结构相同。Ln(III)阴离子也是八面体的。对于 Mn(II)，尽管 Me4N(+)盐是八面体的，但 Et4N(+)盐 Mn(NCS)5具有扭曲的三角双锥几何形状。对于 (Et4N)3[Fe(NCS)6] 和 (n-Bu4N)3[Fe(NCS)6]，观察到从红色到绿色的固态尺寸依赖性颜色变化，这归因于结晶样品中的光散射现象。
