Structural control at the nanoscale via self-assembly toward ordered and well-defined material hierarchies is a critical aspect for the fabrication of functional nanostructures. Herein, the tunable manipulation of the self-assembly of dithiolene complexes to controlled morphology directed by concentration variation is reported. Dimeric tungsten(V) (1) and molybdenum(V) (2) dithiolene–diamide complexes were synthesized and structurally characterized by the single-crystal X-ray diffraction method. Interestingly, the trans-(W₂S₄) core is present in 1 in contrast to the cis-(Mo₂S₄) core in 2 in these analogous complexes. DFT calculations show that the trans form of 1 is stabilized from its cis form by 8 kcal mol⁻¹, whereas the stable cis form of 2 is stabilized from its trans form by 30 kcal mol⁻¹. This variation in the positional terminal sulfide ligand in 1 and 2 is reflected in the respective lattice packing. Such packing controls the self-assembly process to aggregate into different floral shapes in the nanodomain and on increasing the concentration of 1 or 2 results in nanopolyhedral shapes. Such structural control of concentration-driven self-assemblies provides future opportunities to engineer technologically desired nanostructures with complex architectures.

中文翻译：

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钨钼二硫烯络合物类似物纳米组装的结构控制

通过自组装向有序和明确定义的材料层次结构控制纳米级的结构是制造功能性纳米结构的关键方面。在此，报道了通过浓度变化对二硫烯配合物的自组装进行可调操作以控制形态。合成了二聚钨( V )( 1 )和钼( V )( 2 )二硫烯-二酰胺配合物，并通过单晶X射线衍射法对其结构进行了表征。有趣的是，反式-(W ₂ S ₄ ) 核心存在于1中，而顺式-(Mo₂ S ₄ )在这些类似配合物中的2核心。DFT 计算表明， 1的反式形式从其顺式形式稳定了 8 kcal mol ^-1，而2的稳定顺式形式从其反式形式稳定了 30 kcal mol ^-1。1和2中位置末端硫化物配体的这种变化反映在各自的晶格堆积中。这种堆积控制自组装过程以在纳米域中聚集成不同的花形，并增加1或2导致纳米多面体形状。这种浓度驱动自组装的结构控制为未来设计具有复杂结构的技术所需纳米结构提供了机会。