Pacholak Piotr, Gontarczyk Krzysztof, Kamiński Radosław, Durka Krzysztof, Luliński Sergiusz
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland.
Department of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089, Warsaw, Poland.
Chemistry. 2020 Oct 6;26(56):12758-12768. doi: 10.1002/chem.202001960. Epub 2020 Sep 1.
Two covalent organic frameworks comprising Lewis basic P centers and Lewis acidic boron atoms were prepared by poly-condensation reactions of newly obtained tris(4-diisopropoxyborylphenyl)phosphine with 2,3,6,7,10,11-hexahydroxytriphenylene and 2,3,6,7-tetrahydroxy-9,10-dimethylanthracene. Obtained materials exhibit significant sorption of dihydrogen (100 cm g at 1 bar at 77 K), methane (20 cm g at 1 bar at 273 K) and carbon dioxide (50 cm g at 1 bar at 273 K). They were exploited as solid-state ligands for coordination of Pd centers. Alternatively, in a bottom-up approach, boronated phosphine was treated with Pd dba and poly-condensated, yielding hybrid materials where the polymer networks are formed by means of covalent boronate linkages and coordination P-Pd bonds. In addition, the analogous materials based on phosphine oxide were synthesized. The DFT calculations on framework-guest interactions revealed that the behavior of adjacent boron and phosphorus/phosphine oxide centers is reminiscent of that found in Frustrated Lewis Pairs and may improve sorption of selected molecules.
通过新合成的三（4-二异丙氧基硼苯基）膦与2,3,6,7,10,11-六羟基三亚苯和2,3,6,7-四羟基-9,10-二甲基蒽的缩聚反应，制备了两种包含路易斯碱性磷中心和路易斯酸性硼原子的共价有机框架。所得到的材料对氢气（77K、1巴下为100 cm³ g）、甲烷（273K、1巴下为20 cm³ g）和二氧化碳（273K、1巴下为50 cm³ g）表现出显著的吸附性能。它们被用作钯中心配位的固态配体。另外，采用自下而上的方法，将硼化膦与钯二亚苄基丙酮进行处理并缩聚，得到杂化材料，其中聚合物网络通过共价硼酸酯键和配位P-Pd键形成。此外，还合成了基于氧化膦的类似材料。对框架-客体相互作用的密度泛函理论计算表明，相邻硼和磷/氧化膦中心的行为让人联想到受阻路易斯酸碱对中的情况，并且可能改善对特定分子的吸附。
