3D Metal–Organic Framework Based on a Lower-Rim Acid-Functionalized Calix[4]arene: Crystal-to-Crystal Transformation upon Lattice Solvent Removal

Abstract

A rare three-dimensional (3D) calix [4]arene-based metal−organic framework (calixMOF) {[Pb 2 @L]·2DMF} n (1) was obtained by the solvothermal reaction between a lower-rim acidfunctionalized calix [4]arene (H 4 L) and Pb(NO 3 ) 2 in N,Ndimethylformamide; 1 exhibited ths topology, in which Pb(II) atoms accommodated inside the calixarene unit adopted hemidirected coordination geometry. Interestingly, upon the removal of guest solvent molecules, the 3D framework of 1 readily converted to a shrunken 3D framework [Pb 2 @L] n (1a) via a single-crystal to single-crystal transformation. However, the resolvation of the guest molecules was not observed when 1a was immersed into DMF at room temperature or at 110°C. Furthermore, 1a exhibited interesting CO 2 sorption behavior: Its CO 2 isotherm curves exhibited looped patterns of linear adsorption and nonlinear desorption. The thermal behavior and solid-state photoluminescence properties of 1 and 1a were also reported.T he design and construction of metal−organic frameworks (MOFs) has become one of the most rapidly growing topics in supramolecular chemistry because of the potential applications of MOFs in catalysis, 1−3 gas storage, 4−8 and separation. 9−11 Recently, along with the development of MOFs, calix[4]arene-based MOFs (calixMOFs) obtained by the solvothermal reaction of calix[4]arene derivatives with metal ions have become a topic of increasing attention in supramolecular chemistry. This increasing focus is attributed to the fact that calixMOFs as well as the cavities of the calixarene building blocks have large porosities, which are available for applications such as gas uptake. 12−17 Thus far, only calixMOFs having two-dimensional (2D) and three-dimensional (3D) networks, which are constructed by the reaction between "upper"-rim-functionalized calix[4]arenes and transition metal ions, have been reported. 18−32 In contrast, relatively rare examples of calixMOFs based on "lower"-rim-functionalized calix[4]arenes have been found. 33−42 Furthermore, a majority of these calixMOFs are one-dimensional (1D) nanotube-or chain-like coordination polymers, attributed to the use of calix[4]arene derivatives adopting a cone or partial cone conformation. 33−38 Redshaw and co-workers have reported 2D calixMOFs containing lowerrim-functionalized calix[4]arene with a cone conformation. 39 In such 2D calixMOFs, because of the assistance of bridging dipyridyl coligands such as 4,4′-bipyridine, 1,2-di(4-pyridyl)-ethylene, and 4,4′-azopyridine, 2D frameworks are formed, despite the use of calix[4]arene with the cone conformation. Thus far, Che's and Zaworotko's groups have reported only three examples of 3D calixMOFs using the lower-rimfunctionalized calix[4]arene. 40−42 These 3D calixMOFs are constructed using a 1,3-alternative form of calix[4]arene, not the cone conformation.On the basis of the above-mentioned considerations, the lower-rim-functionalized calix[4]arene with the 1,3-alternative conformation can be more favorable than those with the cone conformation for the constructi...

Coordination Polymers based on calixarene derivatives: Structures and properties

“…The combination of ligand L39 with Pb(NO3)2 leads to the formation of a 3D Coordination Polymer of formula [Pb2(L39)]•2DMF presenting a ths topology (figure 39 e) [81]. Interestingly, the 3D system exhibits reversible solvation and desolvation process, together with interesting CO2 adsorption behaviour and luminescent properties.…”

A Metal–Organic Framework Based on a Tetra-Arylextended Calix[4]pyrrole Ligand: Structure Control through the Covalent Connectivity of the Linker

“…However, only theoretical simulations were performed due to lack of success in the activation of the synthesized assemblies. In this context, Park et al 23 reported the synthesis and subsequent activation of a [(Pb2@L)  2 DMF]n MOF, where L is a carboxylic acidfunctionalized calix [4]arene, which involves a single-crystal to single-crystal transformation upon solvent removal.…”

Eine Calixaren‐basierte Metall‐organische Gerüstverbindung für den hoch selektiven NO2‐Nachweis

“…In dieser Zuschrift zeigen wir, dass die hybride Natur eines Metall-organischen Gerüstes (MOF) basierend auf Zirconium-haltigen anorganischen Bausteinen (IBUs), die zwischen sich Calixaren-Linker exponieren, elegant für diese Zwecke dienen kann. [27] Fürd ie Synthese des neuen MOF wurde ZrCl 4 in N,N-Dimethylformamid (DMF) gelçst und Ameisen-, Essig-oder Propionsäure als Modulatoren dazugegeben. [16] Die Porosität, die kontrollierbare Funktionalitätdes Porensystems und die große Zahl an mçglichen Strukturen führt zu MOFs,d ie genau auf ihre potentielle Anwendung zugeschnitten werden kçnnen.…”

“…

Eine Calixaren-basierte Metall-organische [Zr 6 O 4 (OH) 4 (FA) 6 ] 2 (cal) 3 ], FA = Formiat, cal = 1, 26,27,methoxy]-calixaren) wurde synthetisiert und ihre Struktur über Einkristallrçntgendiffraktometrie bestimmt. Das dreidimensionale Gerüst kristallisiert in einem 4,6-verbundenen Netzwerk in der gar-Topologie und weist zwei identische, nichtm iteinander verbundene Porensysteme auf.D ie spezifische BET-Oberflächeb eträgt 670 m 2 g À1 und die Kavitäten der Calixarene sind über das Porensystem zugänglich.

…”

“…Der Linker wurde bereits vorher in MOF-Synthesen verwendet, allerdings führten diese Synthesen nur zu rçhrenfçrmigen Koordinationspolymeren oder zu nicht-porçsen dreidimensionalen MOFs. [27] Fürd ie Synthese des neuen MOF wurde ZrCl 4 in N,N-Dimethylformamid (DMF) gelçst und Ameisen-, Essig-oder Propionsäure als Modulatoren dazugegeben. [28] Nach der Zugabe des Calixaren-Linkers H 4 cal (Abbildung 1a)fand die Kristallisation in einem vorgeheizten Ofen bei 120 8 8Cs tatt (vgl.…”