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首页> 外文期刊>Zeitschrift fur Naturforschung, B. A Journal of Chemical Sciences >Synthesis, structure determination, and magnetic properties of[Cr _3(dpa)_4Cl _2][CuCl _2], a compound comprising a trinuclear chain cation
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Synthesis, structure determination, and magnetic properties of[Cr _3(dpa)_4Cl _2][CuCl _2], a compound comprising a trinuclear chain cation

机译:包含三核链阳离子的化合物[Cr _3(dpa)_4Cl _2] [CuCl _2]的合成,结构确定和磁性

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摘要

The new compound[Cr _3(dpa)_4Cl _2][CuCl _2](1)(dpa = di-2, 2'-pyridylamido)was synthesized by reacting Cr _2(dpa)_4 and anhydrous CuCl2 in dry tetrahydrofuran. Partial oxidation of Cr _2(dpa)_4 by Cu(II)forms Cr _3+ ions, which coordinate to the free N donor atoms of the dpa ligands, and led to the formation of a trinuclear chain cation[Cr _3(dpa)_4Cl _3]~+. Recrystallization from CH _2Cl _2/ethyl ether yielded dark-brown, block-shaped crystals suitable for X-ray structure determination(Pccn(no. 56), a=1246:8(5), b=1487:3(3), c=2184:8(1)pm, V =4051:6(8).10 ~6 pm ~3, Z =4). The crystal structure is composed of discrete[Cr _3(dpa)_4Cl _2]~+ cations and[CuCl _2]~- anions. The Cr _3 chain comprises quadruply-bonded diamagnetic(Cr +2)~(4+)dimers and a pseudo-octahedrally coordinated, paramagnetic Cr ~(3+)ion, manifesting itself in the effective magnetic moment μ _(eff)of 3:54μ B(d ~3, S = 3=2)and the almost ideal Curie-paramagnetic behavior observed between 2 and 300 K with a Weiss constant q = -0:25(4)K and χ _0 = 4:9(7)×10 ~(-4)emu mol ~(-1).
机译:通过在干燥的四氢呋喃中使Cr _2(dpa)_4与无水CuCl2反应,合成了新化合物[Cr _3(dpa)_4Cl _2] [CuCl _2](1)(dpa = di-2,2'-吡啶基酰胺基)。 Cu(II)对Cr _2(dpa)_4的部分氧化形成Cr _3 +离子,这些离子与dpa配体的游离N供体原子配位,并导致形成三核链阳离子[Cr _3(dpa)_4Cl _3 ]〜+。从CH _2Cl _2 /乙醚中重结晶,得到适合于X射线结构测定的深棕色块状晶体(Pccn(no。56),a = 1246:8(5),b = 1487:3(3), c = 2184:8(1)pm,V = 4051:6(8).10〜6 pm〜3,Z = 4)。晶体结构由离散的[Cr _3(dpa)_4Cl _2]〜+阳离子和[CuCl _2]〜-阴离子组成。 Cr _3链包含四重键合的抗磁性(Cr +2)〜(4+)二聚体和拟八面体配位的顺磁性Cr〜(3+)离子,其自身的有效磁矩μ_(eff)为3 :54μB(d〜3,S = 3 = 2),在2至300 K之间观察到几乎理想的居里顺磁行为,Weiss常数为q = -0:25(4)K和χ_0 = 4:9( 7)×10〜(-4)emol mol〜(-1)。

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