Department of Chemistry, University of Science and Technology Beijing, Beijing, 100083, China.
Dalton Trans. 2010 Feb 7;39(5):1321-7. doi: 10.1039/b911178f. Epub 2009 Nov 26.
Homoleptic octa-alpha-substituted bis(phthalocyaninato) rare earth double-deckers HM(III)Pc(alpha-OC(4)H(9))(8) [M = Eu (1), Y (2); Pc(alpha-OC(4)H(9))(8) = 1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyanine] have been prepared by treating the metal-free phthalocyanine H(2)Pc(alpha-OC(4)H(9))(8) with the corresponding M(acac)(3).nH(2)O (acac = acetylacetonate) in the presence of organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and benzo-18-crown-6/benzo-15-crown-5 in refluxing n-octanol. To the best of our knowledge, it is the first example of homoleptic non-peripherally octa(alkoxyl)-substituted bis(phthalocyaninato) rare earth complexes. Comparative studies on a series of reactions reveal the key role of DBU as catalyst and crown ether as template in the formation of homoleptic rare earth double-decker complexes with structurally highly deformed non-peripherally octa(butyloxy)-substituted phthalocyanine ligand. The molecular structure of complex 1 has been determined by single-crystal X-ray diffraction analysis. The metal center is octa-coordinated by the isoindole nitrogen atoms of the two phthalocyaninato ligands, forming a distorted square antiprism. Despite the extremely non-planar saddle conformation employed by metal free H(2)Pc(alpha-OC(4)H(9))(8) molecule, both the phthalocyanine rings in HEu(III)Pc(alpha-OC(4)H(9))(8) (1) adopt a conformation that is domed toward the europium center, similar to corresponding unsubstituted or beta-substituted bis(phthalocyaninato) analogues. These two bis(phthalocyaninato) rare earth double-deckers have also been characterized by a wide range of spectroscopic methods including MS, (1)H NMR, UV-vis, IR, and EPR. Structural and spectroscopic studies reveal that the pi-pi interaction between the two Pc(alpha-OC(4)H(9))(8) rings is weaker than that for the corresponding unsubstituted or beta-substituted bis(phthalocyaninato) analogues.
具有均八取代基的双（酞菁基）稀土双层配合物 HM(III)Pc(alpha-OC(4)H(9))(8) [M = Eu (1), Y (2); Pc(alpha-OC(4)H(9))(8) = 1,4,8,11,15,18,22,25-辛基（4H-9）]（1）通过处理金属酞菁 H(2)Pc(alpha-OC(4)H(9))(8) 与相应的 M(acac)(3).nH(2)O（acac = 乙酰丙酮），在有机碱 1,8-二氮杂二环[5.4.0]十一碳-7-烯（DBU）和 18-冠-6/15-冠-5 的存在下，在回流的正辛醇中合成。据我们所知，这是首例具有均八取代基的非外围全取代双（酞菁基）稀土配合物。对一系列反应的比较研究揭示了 DBU 作为催化剂和冠醚作为模板在形成具有结构高度变形的非外围全取代基的酞菁配体的均八取代基的稀土双层配合物中的关键作用。配合物 1 的分子结构通过单晶 X 射线衍射分析确定。金属中心被两个酞菁配体的异吲哚氮原子八配位，形成扭曲的四方反棱柱体。尽管金属自由 H(2)Pc(alpha-OC(4)H(9))(8)分子采用极其非平面的鞍形构象，但在 HEu(III)Pc(alpha-OC(4)H(9))(8)（1）中，两个酞菁环都采用向镧系元素中心凸起的构象，类似于相应的未取代或β取代的双（酞菁基）类似物。这两种双（酞菁基）稀土双层配合物还通过包括 MS、（1）H NMR、UV-vis、IR 和 EPR 在内的各种光谱方法进行了表征。结构和光谱研究表明，两个 Pc(alpha-OC(4)H(9))(8)环之间的π-π相互作用比相应的未取代或β取代的双（酞菁基）类似物弱。
