Influence of Interpenetration in Diamondoid Metal–Organic Frameworks on the Photoreactivity and Sensing Properties

Abstract

The degree of interpenetration is known to influence the gas sorption, catalytic, magnetic and nonlinear optical properties, chirality, and sensing of various molecules but not the solid-state [2 + 2] photocycloaddition reaction. In our previous studies of a solvothermal reaction using dimethylacetamide (DMA) as one of the solvents, a photoreactive 6-fold interpenetrated metal−organic framework with dia topology, [Zn(bpeb)(bdc)] (1) [bpeb = 1,4-bis[2-(4′-pyridyl)ethenyl]benzene; bdc = 1,4-benzenecarboxylate], was isolated. Because of the slip-stacked alignment of a dipyridyl ligand with two conjugated olefin bonds, the [2 + 2] cycloaddition reaction occurs under UV light leading to the formation of an organic polymer ligand fused with a coordination polymer, 2. On the contrary, under similar conditions when diethylformamide was used instead of DMA, a 5-fold interpenetrated structure, 3, with the same dia topology was obtained in this work. This has been found to be photostable as also predicted from the analysis of the solid state structure. All the solids show interesting photoluminescence properties, and the emissions were preferentially quenched by curcumin to make these materials as potentially useful sensing agents.

A Sensitive Luminescent Acetylacetone Probe Based on Zn‐MOF with Six‐Fold Interpenetration

“…In 1998, aw ide range of interpenetrating frameworks were reported by Batten and Robson. [33] Nevertheless, it is still ac hallenge for us to constructi nterpenetrating networks with novel topology.A sf ar as we know,m ost topology types of sixfold interpenetrating networks reporteda re of either the dia net or chiral net, [34][35][36][37][38][39][40][41] as well as af ew other nets, such as cdl; [42] pts, [43] honeycomb [44] and helical net. [45] Moreover,a lthoughm any sqc networks have been obtained, most of them are three-fold or without interpenetration [46] .H owever,t ot he best of our knowledge, there is no report on six-fold interpenetration with the topology of sqc6.C ompared with the other structures, compound 1 reveals au nique six-foldi nterpenetration with an unusual[ 2 + +2+ +2] mode.…”

Isomerism in double-pillared-layer coordination polymers – structures and photoreactivity

“…These isomers are expected to have similar energies and are likely to be kinetic products. The MOF with diamondoid topology reported previously is also a supramolecular isomer to (1)-(3), this could be considered as the thermodynamic product (Park, Chanthapally et al, 2014;Park et al 2016). We have not found suitable experimental conditions to synthesize (3) exclusively despite many attempts.…”

Solvent‐Mediated Synthesis of Cyclobutane Isomers in a Photoactive Cadmium(II) Porous Coordination Polymer

“…[14][15][16] Metalorganic frameworks (MOFs) and coordination polymers (CPs) have been widely used to control the arrangement of organic molecules in the solid state due to their versatile but highly predictable geometries. [17][18][19][20][21][22][23][24][25] Frameworks that undergo photodimerization through cycloaddition have also displayed favorable gas separation, fluorescence-switching and nitrosensing properties. [26][27][28][29][30][31] Thel igand 1,4-bis[2-(4-pyridyl)ethenyl]benzene (bpeb, Scheme 1) is often used in the synthesis of photoactive MOFs since it has two C=Colefinic bonds.T wo bpeb ligands can align in either an out-of-phase or an in-phase fashion.…”

“…[13] It is an ongoing challenge to control the packing of olefinic molecules to meet these topochemical requirements.T he use of template molecules has proven especially effective in controlling [2+ +2] cycloaddition in the solid state. [17][18][19][20][21][22][23][24][25] Frameworks that undergo photodimerization through cycloaddition have also displayed favorable gas separation, fluorescence-switching and nitrosensing properties. [17][18][19][20][21][22][23][24][25] Frameworks that undergo photodimerization through cycloaddition have also displayed favorable gas separation, fluorescence-switching and nitrosensing properties.…”