Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany.
Acta Crystallogr C Struct Chem. 2023 Apr 1;79(Pt 4):118-124. doi: 10.1107/S2053229623001845. Epub 2023 Mar 9.
The ditopic ligand 10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene (TRIP-Py, CHNPSi) binds as a pyridine donor to Ni and as a phosphatriptycene donor towards Pt. The selectivity relies entirely on the Pearson character of the donor sites and the matching hardness of the respective metal cations. The product is the one-dimensional coordination polymer catena-poly[[[dichloridonickel(II)]-bis{μ-10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene}-bis[dichloridoplatinum(II)]-bis{μ-10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene}] dichloromethane pentasolvate ethanol icosasolvate], {[NiPtCl(TRIP-Py)]·5CHCl·20EtOH} (1), which retains large pores due to the inherent rigidity of the ligand. This is enabled by the caged triptycene scaffold which fixes the direction of the phosphorus donor with respect to the remaining molecule and especially the pyridyl moiety. In its crystal structure, which was determined from synchrotron data, the pores of the polymer are filled with dichloromethane and ethanol molecules. Finding a suitable model for the pore content is complicated as it is too disordered to give a reasonable atomic model but too ordered to be described by an electron gas solvent mask. This article presents an in-depth description of this polymer, as well as a discussion on the use of the bypass algorithm for solvent masks.
双齿配体 10-[4-(吡啶-4-基)苯基]-9-磷杂-10-硅杂三苯并膦(TRIP-Py,CHNPSi)作为吡啶供体与 Ni 配位,作为磷杂三苯并膦供体与 Pt 配位。这种选择性完全依赖于供体位点的 Pearson 特征和相应金属阳离子的匹配硬度。产物是一维配位聚合物 catena-poly[[[二氯镍(II)]-双{μ-10-[4-(吡啶-4-基)苯基]-9-磷杂-10-硅杂三苯并膦}-双[二氯二铂(II)]-双{μ-10-[4-(吡啶-4-基)苯基]-9-磷杂-10-硅杂三苯并膦}]二氯甲烷五溶剂化物乙醇二十溶剂化物],{[NiPtCl(TRIP-Py)]·5CHCl·20EtOH}(1),由于配体的固有刚性,它保留了大孔。这是通过笼状三苯并芴支架实现的,该支架固定了磷供体相对于其余分子尤其是吡啶部分的方向。在其晶体结构中,该聚合物的孔填充了二氯甲烷和乙醇分子。找到合适的孔内容模型很复杂,因为它太无序,无法给出合理的原子模型,但又太有序,无法用电子气溶剂掩蔽来描述。本文对这种聚合物进行了深入描述,并讨论了溶剂掩蔽的旁路算法的使用。