New Early Transition Metal Atom Cluster Materials: In and with Ionic Liquids

具有直接金属-金属键的多核过渡金属配位化合物，特别是早期过渡金属原子的六核、八面体单元（M6-簇合物）已经吸引了科学和工业兴趣几十年。随着最近开始的活动与离子液体（IL）的爆发，这一领域似乎是跳跃式启动，因为初步的实验表明，大量的新化合物是可通过使用离子液体在各自的化学反应。在第一个资助期内，我们成功地合成和表征了一些新的前所未有的六核铌簇合物，使用离子液体进行制备。这些包括第一个特征的八面体M6簇合物与内螯合配体的化合物。此外，制备反应是6-8到6-12簇型转化的第一个例子。另一个前所未有的新化合物是（BMIm）2[Nb 6Cl 12（NCS）6{Ag 2Cl}]。这包含不常见的[Ag 2Cl]+阳离子，其形成无机螯合配体NCS-Ag-Cl-Ag-SCN，其也三维地连接相邻的簇单元。为了合成该化合物，开发了扩散技术，其需要粘性离子液体。使用不同的极性有机溶剂是不成功的。使用这种离子液体扩散技术，合成了大量的簇网络化合物，其由异硫氰酸根连接的簇单元组成，所述簇单元通过亲硫的后过渡金属阳离子Ag（I）、Cu（I）或Hg（I）或相同金属的阳离子络合物互连。在含全氟配体的Nb 6簇合物的研究方向上，以弱配位的“簇合物离子液体”为目标，合成了三种八面体外位含三氟乙酸根配体的化合物，并进行了表征。在这三个领域，WP 1：网络结构; WP 2：螯合配体; WP 3：全氟配体，建议继续研究。新的簇网络结构的化学性质应扩展到含EMIm的离子液体，以及试图制备含空隙的簇-MOFs。第三延伸被引导到不同的互连金属离子上，即Au（I）、Ni（II）、Co（II）和Zn（II）。在WP 2中，计划对具有簇内2-氨基乙醇配体的簇化合物进行彻底表征，特别是在空气中的热稳定性方面。此外，在离子液体中使用邻氨基苯酚盐作为配体的制备尝试是预期的。具有低熔点和全氟化羧酸根配体的新Nb 6簇合物旨在使用六甲基胍阳离子代替四甲基胍阳离子获得，从而避免氢键。此外，应进行使用全氟化醇配体的进一步反应。在最后一个工作包WP 4中，铌簇单元将通过在离子液体中的电化学合成获得。

Polynuclear transition metal coordination compounds with direct metal-metal bonds, especially hexanuclear, octahedral units of early transition metal atoms (M6-clusters) have attracted scientific and industrial interest for decades already. With the recently started eruption of activities with ionic liquids (ILs) this field seems to be jump-started again, because preliminary experiments indicate, that a multitude of novel compounds is available through the use of ILs in respective chemical reactions. Within the first funding period we succeeded in the synthesis and characterization of a number of new unprecedented hexanuclear niobium cluster compounds using ionic liquids for the preparations. These comprise the first characterized octahedral M6 cluster compounds with intra-chelate ligands. Also, the preparative reaction is the first example of a 6-8 to 6-12 cluster type transformation. Another unprecedented new compound is (BMIm)2[Nb6Cl12(NCS)6{Ag2Cl}]. This contains uncommon [Ag2Cl]+ cations, which form inorganic chelate ligands NCS-Ag-Cl-Ag-SCN, which also connect neighbouring cluster units three-dimensionally. For the synthesis of this compound a diffusion technique was developed, which requires viscous ionic liquids. Using different polar organic solvents is not successful. Using this ionic liquid diffusion technique, a larger number of cluster network compounds was synthesized, which consist of iso-thiocyanato ligated cluster units, which are interconnected through the thiophilic late transition metal cations Ag(I), Cu(I), or Hg(I) or cationic complexes of the same metals. In the research direction of Nb6 cluster compounds with perfluorinated ligands, aiming for weakly coordinating 'cluster ionic liquids', three compounds with trifluoroacetato ligands on the octahedral exo sites were synthesized and characterized. The research in these three fields, WP1: network structures; WP2: chelate ligands; WP3: perfluorinated ligands, is proposed to be continued. The chemistry of the new cluster network structures shall be extended onto EMIm containing ionic liquids, as well as towards attempts to prepare void containing cluster-MOFs. A third extension is directed onto different interconnecting metal ions, i.e. Au(I), Ni(II), Co(II), and Zn(II). Within WP2 a thorough characterization of the cluster compound with intra-cluster 2-aminoethanolato ligands is planned to be done, especially with respect to thermal stability in air. Furthermore, preparative attempts in ionic liquids using o-aminophenolate as ligand are intended. New Nb6 cluster compounds with low melting points and perfluorinated carboxylato ligands are intended to be obtained using hexamethylguanidinium cations instead of tetramethylguanidinium, thereby avoiding hydrogen bonding. Also, further reactions using perfluorinated alcoholato ligands shall be done. In the last working package, WP4, niobium cluster units shall be obtained through electrochemical synthesis in ionic liquids.