Janczak Jan, Kubiak Ryszard, Jezierski Adam
W. Trzebiatowski Institute of Low Temperature and Structure Research, Polish Academy of Sciences, 2 Okólna Str., P.O. Box 1410, 50-950 Wroclaw, Poland, and Institute of Chemistry, University of Wroclaw, 14 F. Joliot-Curie Str., 50-383 Wroclaw, Poland.
Inorg Chem. 1999 May 3;38(9):2043-2049. doi: 10.1021/ic981168c.
Crystals of C(64)H(32)N(16)YbI(2) and C(64)H(32)N(16)AsI(2) were grown directly in the reaction of ytterbium or arsenic powder with 1,2-dicyanobenzene under a stream of iodine at 200 degrees C. Both partially oxidized phthalocyanine complexes crystallize in the P4/mcc space group of the tetragonal system with one molecule per unit cell, with the cell dimensions a = 13.927(2) Å, c = 6.409(1) Å, and a = 13.926(2) Å, c = 6.433(1) Å for the Yb and As complexes, respectively. The space group of P4/mcc requires that both heavy (iodine and metal) atoms are disordered in these structures. The structures show columnar pseudo-monodimensional stacks of [YbPc(2)] or [(AsPc)(Pc)] units with an average nonintegral charge of +(2)/(3) and linear chains of triiodide I(3)(-) ions, which were detected by Raman spectroscopy. The monodimensional chains of I(3)(-) ions and pseudo-monodimensional aggregates of YbPc(2) or (AsPc)(Pc) are aligned along the c-axis of the crystals. The Yb(3+) ion lies in the center, whereas in the [(AsPc)(Pc)] unit the As(3+) ion does not lie in the center between the Pc rings. In the crystal of [(AsPc)(Pc)]I(2) both components in the (AsPc)(Pc) unit (e.g., AsPc and Pc) with opposite charge are electrostatically interacting. The magnetic susceptibility measurement of the [YbPc(2)]I(2) shows typical Curie-Weiss behavior, and the effective magnetic moment is about 4.60 &mgr;(B). The EPR measurement shows no signal for the Yb complex, while for [(AsPc)(Pc)]I(2) two signals are observed: a sharp narrow line at g = 2.0028 of width approximately 2 G and a broad line at g = 2.0036 of width approximately 9 G. The two EPR signals are associated with two different radical components: a phthalocyaninato (Pc(-)()) ring and [AsPc(-)()], respectively. Both free radicals are in resonance: [(As(3+)Pc(2)(-))(Pc(-)())] <--> [(As(3+)Pc(-)())(Pc(2)(-))]. Oxygen effects on the EPR signal of the [(AsPc)(Pc)]I(2) crystal have been detected. The conductivity measured on polycrystalline samples at room temperature equals 2.5-4 x 10(-)(2) and 2.2-3.5 x 10(-)(4) Omega(-)(1) cm(-)(1) for [YbPc(2)]I(2) and [AsPc(Pc)]I(2), respectively. Both complexes exhibit nonmetallic character in conductivity (dsigma/dT > 0).
C(64)H(32)N(16)YbI(2)和C(64)H(32)N(16)AsI(2)晶体是在200℃碘气流下，通过镱或砷粉与1,2 - 二氰基苯直接反应生长得到的。两种部分氧化的酞菁配合物均以四方晶系的P4/mcc空间群结晶，每个晶胞中有一个分子，对于Yb配合物，晶胞参数为a = 13.927(2) Å，c = 6.409(1) Å；对于As配合物，晶胞参数为a = 13.926(2) Å，c = 6.433(1) Å。P4/mcc空间群要求在这些结构中两个重原子（碘和金属）都是无序的。结构显示出[YbPc(2)]或[(AsPc)(Pc)]单元的柱状准一维堆叠，平均非整电荷为+(2)/(3)，以及通过拉曼光谱检测到的三碘化物I(3)(-)离子的线性链。I(3)(-)离子的一维链和YbPc(2)或(AsPc)(Pc)的准一维聚集体沿晶体的c轴排列。Yb(3+)离子位于中心，而在[(AsPc)(Pc)]单元中，As(3+)离子不在酞菁环之间的中心位置。在[(AsPc)(Pc)]I(2)晶体中，(AsPc)(Pc)单元中带相反电荷的两个组分（例如AsPc和Pc）存在静电相互作用。[YbPc(2)]I(2)的磁化率测量显示出典型的居里 - 外斯行为，有效磁矩约为4.60 μ(B)。电子顺磁共振测量表明Yb配合物没有信号，而对于[(AsPc)(Pc)]I(2)观察到两个信号：一个在g = 2.0028处的尖锐窄线，宽度约为2 G，另一个在g = 2.0036处的宽线，宽度约为9 G。这两个电子顺磁共振信号分别与两个不同的自由基组分相关：一个酞菁基（Pc(-)()）环和[AsPc(-)()]。两个自由基处于共振状态：[(As(3+)Pc(2)(-))(Pc(-)())] <--> [(As(3+)Pc(-)())(Pc(2)(-))]。已经检测到氧气对[(AsPc)(Pc)]I(2)晶体的电子顺磁共振信号的影响。在室温下对多晶样品测量的电导率，对于[YbPc(2)]I(2)和[AsPc(Pc)]I(2)分别为2.5 - 至4×10(-)(2)和2.2 - 至3.5×10(-)(4) Ω(-)(1) cm(-)(1)。两种配合物在电导率方面均表现出非金属特性（dsigma/dT > 0）。
