Bolivar-Pineda Lina M, Mendoza-Domínguez Carlos U, Rudolf Petra, Basiuk Elena V, Basiuk Vladimir A
Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C.U., Ciudad de México 04510, Mexico.
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
Molecules. 2024 Jun 6;29(11):2690. doi: 10.3390/molecules29112690.
Rare earth bisphthalocyanines (MPc) are of particular interest because of their behavior as single-molecular magnets, which makes them suitable for applications in molecular spintronics, high-density data storage and quantum computation. Nevertheless, MPc are not commercially available, and the synthesis routes are mainly focused on obtaining substituted phthalocyanines. Two preparation routes depend on the precursor: synthesis from phthalonitrile (PN) and the metalation of free or dilithium phthalocyanine (HPc and LiPc). In both options, byproducts such as free-base phthalocyanine and in the first route additional PN oligomers are generated, which influence the MPc yield. There are three preparation methods for these routes: heating, microwave radiation and reflux. In this research, solvothermal synthesis was applied as a new approach to prepare yttrium, lanthanum, gadolinium and terbium unsubstituted bisphthalocyanines using LiPc and the rare earth(III) acetylacetonates. Purification by sublimation gave high product yields compared to those reported, namely 68% for YPc, 43% for LaPc, 63% for GdPc and 62% for TbPc, without any detectable presence of HPc. Characterization by infrared, Raman, ultraviolet-visible and X-ray photoelectron spectroscopy as well as elemental analysis revealed the main featuresof the four bisphthalocyanines, indicating the success of the synthesis of the complexes.
稀土双酞菁（MPc）因其作为单分子磁体的特性而备受关注，这使其适用于分子自旋电子学、高密度数据存储和量子计算等领域。然而，MPc尚无商业供应，其合成路线主要集中在获得取代酞菁上。两种制备路线取决于前驱体：由邻苯二甲腈（PN）合成以及游离或二锂酞菁（HPc和LiPc）的金属化。在这两种方法中，都会产生诸如游离碱酞菁等副产物，并且在第一种路线中还会生成额外的PN低聚物，这会影响MPc的产率。这些路线有三种制备方法：加热、微波辐射和回流。在本研究中，采用溶剂热合成法作为一种新方法，使用LiPc和稀土（III）乙酰丙酮盐制备钇、镧、钆和铽的未取代双酞菁。与报道的产率相比，升华纯化得到了较高的产物产率，即YPc为68%，LaPc为43%，GdPc为63%，TbPc为62%，且未检测到HPc的存在。通过红外、拉曼、紫外可见和X射线光电子能谱以及元素分析对其进行表征，揭示了四种双酞菁的主要特征，表明配合物的合成成功。
