Tailoring stability, catalytic activity and selectivity of covalent metal–organic frameworks via steric modification of metal nodes

Abstract

Although many efforts have been paid to tune catalytic performance via the modification of MOF nodes including metal exchange, defect creation and metal insertion, the steric tuning on MOF nodes...

A Photosensitizing Metal–Organic Framework as a Tandem Reaction Catalyst for Primary Alcohols from Terminal Alkenes and Alkynes

“…Moreover, the deuterium‐labelling experiments (Figures S21–S25) confirm water molecules as the proton sources for the hydroboration reaction at internal carbons, in good agreement with our previous report [11e] . Based on these control experiments and the previously reported examples, [9a, 10c, 11c, 12, 20] a reaction mechanism was proposed as shown in Figure 4. Generally, the B−B bond cleavage of B 2 Pin 2 was firstly triggered in the presence of the base, and the BPin species was bonded to the N‐site of the pyrazole group in the CTU.…”

“…The combination of other copper sources and 2 only gave a yield of 15 % and 25 %, respectively (Table 1, entries 11, 12), implying the Cu‐CTU plays a crucial role during the catalytic cycles. When JNM‐1 [11e] or JNM‐5 [12] was used as catalysts, 4 a can be obtained with a low yield of 23 % or 7 %, respectively (Table 1, entries 13, 14), suggesting the Bodipy linkers are important for photocatalytic oxidation of organoboron. Furthermore, a large‐scale reaction involving 10 g of 3 a with low catalyst loading (0.47 mol % JNM‐20 ) was conducted.…”

“…We have previously reported a series of cyclic trinuclear copper(I) units (Cu‐CTUs) based two‐dimensional (2D) covalent metal–organic frameworks (CMOFs) by combining the chemistry of covalent‐organic frameworks (COF) and MOFs [11, 12] . It has been found that the Cu‐CTUs in CMOFs can act as active sites for catalyzing the hydroboration of terminal alkynes and alkenes, respectively [11e, 12] . In addition, we recently synthesized the first example of Cu‐CTU photosensitizer from a boron dipyrromethene (Bodipy) based ligand.…”

A Photosensitizing Metal–Organic Framework as a Tandem Reaction Catalyst for Primary Alcohols from Terminal Alkenes and Alkynes

“…The combination of other copper sources and 2 only gave a yield of 15 % and 25 %, respectively (Table 1, entries 11, 12), implying the Cu-CTU plays a crucial role during the catalytic cycles. When JNM-1 [11e] or JNM-5 [12] was used as catalysts, 4 a can be obtained with a low yield of 23 % or 7 %, respectively (Table 1, entries 13, 14), suggesting the Bodipy linkers are important for photocatalytic oxidation of organoboron. Furthermore, a large-scale reaction involving 10 g of 3 a with low catalyst loading (0.47 mol % JNM-20) was conducted.…”

Imine-linked donor–acceptor metal–organic frameworks for an efficient photocatalytic oxidative coupling reaction

“…S9 and S10 †). X-ray photoelectron spectroscopy (XPS) spectra of JNM-18 and JNM-19 revealed symmetrical Cu(I) 2p 3/2 peaks at 932.98 and 932.82 eV without satellite peaks, 38 suggesting the monovalent state of copper ions within the skeleton (Fig. S11 and S12 †).…”