Replication data for: "Olefin Metathesis in Confinement: Towards Covalent Organic Framework Scaffolds for Increased Macrocyclization Selectivity"

Covalent organic frameworks (COFs) offer vast structural and chemical diversity enabling a wide and growing range of applications. While COFs are well-established as heterogeneous catalysts, so far, their high and ordered porosity has scarcely been utilized to its full potential when it comes to spatially confined reactions in COF pores to alter the outcome of reactions. Here, we present a highly porous and crystalline, large-pore COF as catalytic support in α,ω-diene ring-closing metathesis reactions, leading to increased macrocylization selectivity. COF pore-wall modification by immobilization of a Grubbs-Hoveyda-type catalyst via a mild silylation reaction provides a molecularly precise heterogeneous metathesis catalyst. An increased macro(mono)cyclization (MMC) selectivity over oligomerization (O) for the heterogeneous COF-catalyst (MMC:O = 1.35) of up to 51% compared to the homogeneous catalyst (MMC:O = 0.90) was observed along with a substrate-size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement. This dataset contains all data from analytical measurements including FT-IR spectra, raw XRD patterns, 1H and 13C ssNMR and lNMR spectra, TGA, N2 sorption isotherms, pore-size distributions, BET plots, SEm and TEM images, quantum-chemically optimized structures, CIFs of the journal article mentioned under the related publication. Open *.cif and *.xyz files with a visualization software (see http://ww1.iucr.org/iucr-top/cif/), *.raw files with WinXPOW, *.sp files with PerkinElmer Spectrum software, *.mnova files with MestReNova, *.fq/.gr/iq/sq files with a text editor, .qps with ASiQwin, and *.pro files with TOPAS.

共价有机框架（COFs）凭借其丰富的结构和化学多样性，为广泛的日益增长的应用领域提供了可能。虽然COFs作为异相催化剂已得到广泛应用，但截至目前，其在COF孔隙中空间受限反应中的高有序孔径尚未得到充分利用，以改变反应的最终结果。在本研究中，我们提出了一种高孔隙率、结晶度高、大孔径的COF作为α,ω-二烯环加成反应的催化剂载体，从而提高了大环化选择性的选择性。通过温和的硅烷化反应固定Grubbs-Hoveyda型催化剂对COF孔壁进行修饰，提供了一种分子精确的异相转位催化剂。对于异相COF催化剂（MMC：O = 1.35）而言，与均相催化剂（MMC：O = 0.90）相比，观察到更高的宏观（单）环化（MMC）选择性与聚合（O）选择性的比值，高达51%，同时选择性对底物大小的依赖性表明了由孔径限制引起的扩散限制。本数据集包含了所有分析测量数据，包括FT-IR光谱、原始XRD模式、1H和13C固体核磁共振（ssNMR）以及液体核磁共振（lNMR）光谱、热重分析（TGA）、N2吸附等温线、孔径分布、BET图、扫描电子显微镜（SEM）和透射电子显微镜（TEM）图像、量子化学优化结构、相关出版物中提到的期刊文章的CIFs。使用可视化软件打开*.cif和*.xyz文件（参见http://ww1.iucr.org/iucr-top/cif/），使用WinXPOW打开*.raw文件，使用PerkinElmer光谱软件打开*.sp文件，使用MestReNova打开*.mnova文件，使用文本编辑器打开*.fq/.gr/iq/sq文件，使用ASiQwin打开*.qps文件，使用TOPAS打开*.pro文件。