Kusumoto Sotaro, Atoini Youssef, Masuda Shunya, Kim Jee Young, Hayami Shinya, Kim Yang, Harrowfield Jack, Thuéry Pierre
Department of Material & Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan.
Technical University of Munich Campus Straubing, Schulgasse 22, 94315 Straubing, Germany.
Inorg Chem. 2022 Sep 26;61(38):15182-15203. doi: 10.1021/acs.inorgchem.2c02426. Epub 2022 Sep 9.
The three zwitterionic di- and tricarboxylate ligands 1,1'-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-4-carboxylate) (L1), 1,1'-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-3-carboxylate) (L1), and 1,1',1″-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(pyridin-1-ium-4-carboxylate) (L2) have been used as ligands to synthesize a series of 15 uranyl ion complexes involving various anionic coligands, in most cases polycarboxylates. [(UO)(L1)(cbtc)(HO)]·10HO (, cbtc = ,,1,2,3,4-cyclobutanetetracarboxylate) is a discrete, dinuclear ring-shaped complex with a central cbtc pillar. While [UO(L1)(NO)] (), [UO(L1)(OAc)] (), and [UO(L1)(HCOO)] () are simple chains, [(UO)(L1)(1,3-pda)] (, 1,3-pda = 1,3-phenylenediacetate) is a daisy chain and [UO(L1)(pdda)]·10HO (, pdda = 1,2-phenylenedioxydiacetate) is a double-stranded, ribbon-like chain. Both [UO(L1)(pht)]·5HO (, pht = phthalate) and [(UO)(L1)(pht)(OH)] () crystallize as diperiodic networks with the topology, the latter involving hydroxo-bridged trinuclear nodes. [(UO)(L1)(/-1,3-chdc)] (, /-1,3-chdc = /-1,3-cyclohexanedicarboxylate) and [UO(L1)(-1,4-chdc)]·1.5HO (, -1,4-chdc = -1,4-cyclohexanedicarboxylate) are also diperiodic, with the VO and topologies, respectively. Both [(UO)(L1)(/-1,4-chdc)] () and [(UO)(L1)(1,2-pda)] (, 1,2-pda = 1,2-phenylenediacetate) crystallize as diperiodic networks with topology, and they display threefold parallel interpenetration. [HL2][(UO)(L2)(adc)]Br (, adc = 1,3-adamantanedicarboxylate) contains a very corrugated network with two different kinds of cells, and the uncoordinated HL2 molecule associates with the coordinated L2 to form a capsule containing the bromide anion. [(UO)(L1)(kpim)] (, kpim = 4-ketopimelate) is a three-periodic framework with L1 molecules pillaring diperiodic subunits, whereas (UO)(L2)(-1,4-chdc)Br·6HO (), the only cationic complex in the series, is a triperiodic framework with topology and -1,4-chdc anions pillaring diperiodic subunits. Solid-state emission spectra and photoluminescence quantum yields are reported for all complexes.
三种两性离子二羧酸和三羧酸配体，即1,1'-[(2,3,5,6-四甲基苯-1,4-二亚基)双(亚甲基)]双(吡啶-1-鎓-4-羧酸盐)(L1)、1,1'-[(2,3,5,6-四甲基苯-1,4-二亚基)双(亚甲基)]双(吡啶-1-鎓-3-羧酸盐)(L1)和1,1',1″-[(2,4,6-三甲基苯-1,3,5-三亚基)三(亚甲基)]三(吡啶-1-鎓-4-羧酸盐)(L2)，已被用作配体来合成一系列15种铀酰离子配合物，这些配合物涉及各种阴离子共配体，在大多数情况下是多羧酸盐。[(UO)(L1)(cbtc)(HO)]·10HO(，cbtc = ，，1,2,3,4-环丁烷四羧酸盐)是一种离散的双核环状配合物，有一个中心cbtc柱。而UO(L1)(NO)、UO(L1)(OAc)和UO(L1)(HCOO)是简单的链状结构，[(UO)(L1)(1,3-pda)] (，1,3-pda = 1,3-苯二乙酸盐)是一种雏菊链结构，[UO(L1)(pdda)]·10HO(，pdda = 1,2-苯二氧基二乙酸盐)是一种双链的带状链结构。[UO(L1)(pht)]·5HO(，pht = 邻苯二甲酸盐)和(UO)(L1)(pht)(OH)都结晶为具有拓扑结构的双周期网络，后者涉及羟基桥连的三核节点。[(UO)(L1)(/-1,3-chdc)] (，/-1,3-chdc = /-1,3-环己烷二羧酸盐)和[UO(L1)(-1,4-chdc)]·1.5HO(，-1,4-chdc = -1,4-环己烷二羧酸盐)也是双周期的，分别具有VO和拓扑结构。(UO)(L1)(/-1,4-chdc)和[(UO)(L1)(1,2-pda)] (，1,2-pda = 1,2-苯二乙酸盐)都结晶为具有拓扑结构的双周期网络，并且它们呈现三重平行互穿。[HL2][(UO)(L2)(adc)]Br(，adc = 1,3-金刚烷二羧酸盐)包含一个非常褶皱的网络，有两种不同的晶胞，未配位的HL2分子与配位的L2缔合形成一个包含溴离子的胶囊。[(UO)(L1)(kpim)] (，kpim = 4-酮基庚二酸)是一个三周期框架，L1分子支撑着双周期亚基，而(UO)(L2)(-1,4-chdc)Br·6HO()是该系列中唯一的阳离子配合物，是一个具有拓扑结构的三周期框架，-1,4-chdc阴离子支撑着双周期亚基。报告了所有配合物的固态发射光谱和光致发光量子产率。
