The Role of Modulators in Controlling Layer Spacings in a Tritopic Linker Based Zirconium 2D Microporous Coordination Polymer

Abstract

A 2D zirconium-based microporous coordination polymer derived from the tritopic linker 1,3,5-(4-carboxylphenyl)benzene, UMCM-309a, has been synthesized. This noninterpenetrated material possesses a Zr6(μ3-O)4(μ3-OH)4(RCO2)6(OH)6(H2O)6 cluster with six hexagonal-planar-coordinated linkers. UMCM-309a is stable in an aqueous HCl solution for over 4 months. The use of different monocarboxylates as modulators leads to similar 2D structures with different layer spacings; moreover, removal of the modulator yields the parent UMCM-309a.

Single-site metal–organic framework catalysts for the oxidative coupling of arenes via C–H/C–H activation

“…The hexanuclear Zr-clusters of MOF-808 ([Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (btc) 2 (CH 3 COO) 6 ], btc 3– = 1,3,5-benzenetricarboxylate)48,49 are 6-fold coordinated by btc 3– linkers, resulting in up to 6 open sites per cluster, after removing the acetate modulators using a simple acid treatment. A closely related MOF with 6-fold coordinated Zr-clusters is UMCM-309a ([Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (btb) 2 (HCOO) 6 ], btb 3– = 1,3,5-(4-carboxylphenyl)benzene),50 which features a stable two-dimensional layered network instead of a three-dimensional framework. Recently, a new 8-connected Zr-MOF with 3,3′,5,5′-azobenzene-tetracarboxylate (abtc 4– ) linkers ([Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (abtc) 2 (OH) 4 (H 2 O) 4 ]) was reported,51 which contains 4 open sites per cluster and could be synthesized following a newly developed water-based green synthesis procedure (Fig.…”

Metal‐Organic Framework‐Based Catalysts for Oxidative Desulfurization

“…The family of Zr‐MOFs is not limited to the UiO‐66 family, the Zr 6 ‐based MOF‐808 (trimesic acid as linker) and UMCM‐309 (1,3,5‐tris(4‐carboxyphenyl) benzene as linker) were also tested in the ODS of model fuel, using TBHP as oxidant, exhibiting satisfactory performances . Higher surface area and larger pores favor the access of the sulfur compounds to the coordinatively unsaturated zirconium sites, resulting in higher catalytic activity for MOF‐808 than for UMCM‐309.…”

Effect of Benzoic Acid as a Modulator in the Structure of UiO-66: An Experimental and Computational Study

“…Much attention has therefore been given to relatively stable subclasses of MOFs, e.g. zirconium (IV) MOFs, particularly those whose clusters are based on a Zr6 octahedral core [10][11][12][13][14][15] . The most widely studied material among these "Zr6 MOFs" is UiO-66 ( Figure 1), whose Zr6-oxyhydroxide clusters are 12-fold connected by 1,4-benzenedicarboxylate (BDC, a linear ditopic linker), resulting in a highly symmetric face-centered cubic (fcu) structure 12 .…”