Soft crystallization routes for the controlled growth of one- and two-dimensional Cu(II)-coordination polymers of the type [(Cu(hfa)₂)_x(3-tpt)]_n (hfa = hexafluoroacetylacetonate, 3-tpt = 2,4,6-tris(3-pyridyl)-1,3,5-triazine) are described. Three volatile solvents with different protic/aprotic characteristics were chosen as the reaction media, e.g., supercritical CO₂, chloroform, and ethanol. Five (1–5) new compounds were crystallized, with different structures and Cu(II)/3-tpt ratios. The structures of 3-tpt and five new coordination polymers were elucidated by single-crystal synchrotron X-ray diffraction. A description of the crystallization pathways followed for the synthesis of the individual compounds is given based on the protic or aprotic character of the used solvents and reagents’ solubility constraints. The main novelty of the work relies in establishing the foundations of 3-tpt isomeric control during crystallization through solvent selection. From the five precipitated new compounds, 3 displays a significant framework flexibility, associated with N₂ adsorption at low temperature, presenting a stepwise adsorption isotherm. The N₂ adsorption process was followed by in situ synchrotron X-ray powder diffraction.

中文翻译：

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在结晶过程中通过溶剂控制三位三嗪构象来调节配位聚合物的结构和柔韧性

[[Cu（hfa）₂）_x（3-tpt）] _n类型的一维和二维Cu（II）配位聚合物的受控生长的软结晶途径（hfa =六氟乙酰丙酮酸酯，3-tpt = 2描述了，4，6-三（3-吡啶基）-1，3，5-三嗪。选择具有不同质子/非质子特性的三种挥发性溶剂作为反应介质，例如超临界CO ₂，氯仿和乙醇。五（1 – 5）新化合物结晶，具有不同的结构和Cu（II）/ 3-tpt比。通过单晶同步加速器X射线衍射阐明了3-tpt和五种新的配位聚合物的结构。基于所用溶剂的质子或非质子特性以及试剂的溶解度限制，给出了合成各个化合物所遵循的结晶途径的描述。这项工作的主要新颖之处在于通过溶剂选择为结晶过程中建立3-tpt异构体控制奠定了基础。从这五种沉淀的新化合物中，有3种具有显着的骨架柔韧性，与低温下的N ₂吸附有关，呈现出逐步吸附等温线。N ₂吸附过程之后进行原位同步加速器X射线粉末衍射。