A Chemically Functionalizable Nanoporous Material [Cu ₃ (TMA) ₂ (H ₂ O) ₃ ] _n

Abstract

Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240 degreesC.

Sustainable Separations of C4‐Hydrocarbons by Using Microporous Materials

“…Cu 3 (BTC) 2 (BTC=1,3,5,‐benzene‐tricarboxylate), also known as HKUST‐1, is a Lewis acid MOF that has been studied extensively 69, 70. The main structural feature of Cu 3 (BTC) 2 is a Cu 2+ dimer with a Cu 2+ −Cu 2+ distance of 2.63 Å. Twelve carboxylate oxygen atoms from the two BTC ligands bind to the four coordination sites of each of the three Cu 2+ ions.…”

Probing the Lewis Acidity and Catalytic Activity of the Metal–Organic Framework [Cu3(btc)2] (BTC=Benzene‐1,3,5‐tricarboxylate)

“…The free space between the metal clusters and ligands shows up as pores in the eventual structure. [1][2][3][4] In literature, the term MOF covers a wide assembly of hybrid compounds. [4,5] Because of the exceptionally high pore volume and surface area of MOFs, many research efforts have been spent to their application in the sorption of light gases, either as such [6][7][8][9][10] or after modification with, for example, Ba 2 + .…”

“…[Cu 3 A C H T U N G T R E N N U N G (btc) 2 ] is a rigid MOF with a zeolite-like structure and with free coordination sites on the Cu II ion. It contains three types of pores, of which the larger two penetrate the structure in all three dimensions and are connected with pore windows of ca.…”

“…The crystalline material was characterized by X-ray diffraction, optical microscopy, SEM, X-ray photoelectron spectroscopy, N 2 sorption, thermogravimetry, and IR spectroscopy of adsorbed CO. CO adsorbs on a small number of Cu 2 O impurities, and particularly on the free Cu II coordination sites in the framework. [Cu 3 A C H T U N G T R E N N U N G (btc) 2 ] is a highly selective Lewis acid catalyst for the isomerization of terpene derivatives, such as the rearrangement of a-pinene oxide to campholenic aldehyde and the cyclization of citronellal to isopulegol. By using the ethylene ketal of 2-bromopropiophenone as a test substrate, it was demonstrated that the active sites in [Cu 3 A C H T U N G T R E N N U N G (btc) 2 ] are hard Lewis acids.…”

“…[Cu 3 A C H T U N G T R E N N U N G (btc) 2 ] is a highly selective Lewis acid catalyst for the isomerization of terpene derivatives, such as the rearrangement of a-pinene oxide to campholenic aldehyde and the cyclization of citronellal to isopulegol. By using the ethylene ketal of 2-bromopropiophenone as a test substrate, it was demonstrated that the active sites in [Cu 3 A C H T U N G T R E N N U N G (btc) 2 ] are hard Lewis acids. Catalyst stability, re-usability, and heterogeneity are critically assessed.…”