Intercalation of Porphyrin‐Based SURMOF in Layered Eu(III) Hydroxide: An Approach Toward Symbimetic Hybrid Materials

Abstract

A strategy for rational design of synergetic hybrid materials exploiting stabilization of intercalated layered matrices via coordination bonding is described. A new hybrid material is assembled through subsequent intercalation of the surface‐anchored metal–organic framework (SURMOF) components, zinc acetate and 5,10,15,20‐tetrakis(4‐carboxyphenyl)‐porphyrin‐zinc(II) (ZnTCPP), into the layered europium(III) hydroxychloride (LEuH). The formation of the SURMOF clusters intercalated in LEuH is confirmed by X‐ray diffraction, FTIR and Raman spectroscopy, and BET nitrogen absorption methods. The catalytic function of the SURMOF/LEuH hybrid and its components in the model reaction of hydrolysis of bis(4‐nitrophenyl) phosphate in the acidic solution is studied by UV–vis and MALDI‐TOF spectroscopy. Both the non‐intercalated matrix and the MOF powder are inactive and unstable in the substrate solution. Unlike its components, the SURMOF/LEuH hybrid exhibits synergetic catalytic activity increasing with the amount of the intercalated compounds because of the mutual stabilization of the components through coordination interactions. The results provide a basis for symbimetic (mimicking the symbiotic behavior in biological systems) hybrid materials, in which stabilization of functional units in the intercalated structure translates into a synergy of useful properties.

Switchable Nanozyme Activity of Porphyrins Intercalated in Layered Gadolinium Hydroxide

“…Firstly, layered gadolinium hydroxochloride LHGd-Cl was prepared [ 59 ]. According to XRD data ( Figure 1 a), the LHGd-Cl obtained crystallised in an orthorhombic system with unit cell parameters a = 12.88, b = 6.39, c = 8.45 Å, which coincided with the diffraction data for gadolinium hydroxochloride Gd 2 (OH) 5 Cl·nH 2 O [ 24 ].…”

Low-temperature synthesis of NaRE(WO4)2 films via anion exchange from layered rare-earth hydroxides (LRHs) films, phase/morphology evolution and photoluminescence

“…1a, a series of (00l) diffractions and (220) diffraction are the characteristic of RE 2 IJOH) 5 NO 3 •nH 2 O (LRH) compounds. [23][24][25][26][27][28][29][30][31][32][33][34][35][36] According to the structure of LRH, the (220) diffraction is known to have originated from the [RE 2 IJOH) 5 IJH 2 O) n ] + host layer, and the intense and sharp (220) diffraction peak indicates that the host layer of LRH is suitably crystallized.…”

Fabrication of REVO4 films via sacrificial conversion from layered rare-earth hydroxide (LRH) films: the investigation of the transition mechanism and their photoluminescence

“…16 Layered rare-earth hydroxides (LRHs), with a general formula of RE 2 (OH) 5 NO − anions along the c-axis. 17,18 LRHs have attracted extensive attention since they were first reported in 2006 owing to the special layered structure and the properties of rare-earth elements, 19 which include interlayer anion exchange, 18,20,21 catalytic performance of intercalated products, 19,22,23 exfoliation of bulk crystals into nanosheets, [24][25][26] photoluminescence, 18,[26][27][28] and enhancement of luminescence. [29][30][31][32][33][34][35][36][37] Also, the self-assembly of functional films is one of the most attractive aspects of LRHs.…”