Mian Mohammad Rasel, Afrin Unjila, Takaishi Shinya, Breedlove Brian K, Yamashita Masahiro, Iguchi Hiroaki
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-Aoba, Aramaki, Sendai 980-8578, Japan.
School of Materials Science and Engineering, Nankai University, Tianjin 300350, P. R. China.
Dalton Trans. 2023 Oct 31;52(42):15503-15509. doi: 10.1039/d3dt01700a.
New Magnus' green salt (MGS) analogues, [M(dabdOH)][MCl]·2HO (dabdOH = (2,3)-2,3-diaminobutane-1,4-diol; M = Pd (1) and M = Pt(2)), in which [M(dabdOH)] and [MCl] are stacked alternately to form linear chains, were obtained as hexagonal plate crystals. The hexagonal shape and large crystal size are unprecedented features as MGS analogues. An unusual trigonal grade separation of chain complexes has been revealed by the structural analysis. 1 and 2 exhibited remarkable yellow and pink colours, respectively, which are derived from weak M⋯M interactions. The dabdOH ligand, which has an additional hydrogen donor group (hydroxy group), produces a multiple-hydrogen-bond network. The combination of intrachain and interchain hydrogen bonds gives a two-dimensional (2D) hydrogen-bond sheet, and each 2D sheet is indirectly connected by hydrogen bonds lattice water molecules. The OH-functionalised ligand greatly increases the hydrophilicity of the MGS analogues and yields the largest single crystals of all MGS analogues reported so far. The trigonal grade-separated chain structure is likely due to the geometric matching between the periodicity of chains and the short axis width of the chain. This strategy opens up new insight for preparing large crystals of MGS analogues and for constructing trigonal grade-separated nanowires in molecular crystals.
新型马格努斯绿盐（MGS）类似物[M(dabdOH)][MCl]·2H₂O（dabdOH = (2,3)-2,3 - 二氨基丁烷 - 1,4 - 二醇；M = Pd (1) 且 M = Pt(2)），其中[M(dabdOH)]和[MCl]交替堆叠形成线性链，以六方片状晶体形式获得。六方形状和大晶体尺寸作为MGS类似物是前所未有的特征。结构分析揭示了链状配合物不寻常的三角分级分离。1和2分别呈现出显著的黄色和粉色，这源于较弱的M⋯M相互作用。具有额外氢供体基团（羟基）的dabdOH配体形成了多重氢键网络。链内和链间氢键的结合形成了二维（2D）氢键片层，并且每个2D片层通过氢键与晶格水分子间接相连。OH官能化配体极大地增加了MGS类似物的亲水性，并产生了迄今为止报道的所有MGS类似物中最大的单晶。三角分级分离的链结构可能是由于链的周期性与链的短轴宽度之间的几何匹配。这种策略为制备MGS类似物的大晶体以及在分子晶体中构建三角分级分离的纳米线开辟了新的思路。
