Two-dimensional metal–organic layers constructed from Hf₆/Hf₁₂-oxo clusters and a trigonal pyramidal phosphine oxide ligand

Abstract

Metal–organic layer (MOL), a category of two-dimensional materials, has attracted wide interest due to its molecular tunability and the ease for surface modification. Herein we reported the synthesis and structural...

Bridging Homogeneous and Heterogeneous Catalysis: Phosphine‐Functionalized Metal‐Organic Frameworks

“…Recently, Wang group built the metal-organic layers (MOL) with trigonal pyramidal phosphine oxide ligand. [77] In contrast to other MOLs, the Hf 6 oxo clusters were alternately connected with Hf 12 oxo clusters, resulting in wavy 2D structure (Figure 7). Similar topology could be achieved with reduced tris(4carboxylphenyl)phosphine (TPP) ligand, which provide metal coordination sites for catalysis.…”

“…On the other hand, the special non‐planar structure of phosphine promotes the development of new MOFs. Recently, Wang group built the metal‐organic layers (MOL) with trigonal pyramidal phosphine oxide ligand [77] . In contrast to other MOLs, the Hf 6 oxo clusters were alternately connected with Hf 12 oxo clusters, resulting in wavy 2D structure (Figure 7).…”

Phosphine-based metal–organic layers to construct single-site heterogeneous catalysts for arene borylation

“…4,6,7 We recently used a tris-(4-carboxylphenyl)phosphine oxide (TPO) to construct a MOL containing two types of Hf-oxo clusters, namely Hf 6 and Hf 12 . 8 However, attempting to substitute TPO ligand by a phosphine ligand under similar preparation conditions resulted in a MOL with poor crystallinity. It is desirable to obtain a MOL with a free phosphine site, which is crucial for coordinating transition metal centers for catalysis.…”

“…We began by considering a Zr-phosphine oxide-based MOF (TPO-MOF, CCDC 2159729) of known crystal structure. 8 The PQO site coordinates to the Zr 4+ center to construct the 3D structure. If we substituted the phosphine oxide ligand by the phosphine ligand, the PQO-Zr linkage would be cleaved, leaving a 2D structure of separated monolayers.…”