Coordination and Organometallic Polymers and Oligomers of Upper-Rim Functionalized Calix[4]arenes by Transition Metals

Harvey, Pierre D.

doi:10.1007/s10904-004-0761-7

Cited by 20 publications

(1 citation statement)

References 28 publications

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“…The 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, − gas storage, − and separation. − 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. − 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. − …”

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

Lee

Kim

Heo

et al. 2015

Crystal Growth & Design

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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...

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