96392-77-7Relevant articles and documents
Water Sorption Evolution Enabled by Reticular Construction of Zirconium Metal-Organic Frameworks Based on a Unique [2.2]Paracyclophane Scaffold
Chen, Zhijie,Cui, Yong,Farha, Omar K.,Gong, Wei,Idrees, Karam B.,Liu, Yan,Sha, Fanrui,Son, Florencia A.,Xie, Haomiao
supporting information, p. 1826 - 1834 (2022/02/01)
Water vapor sorption by metal-organic frameworks (MOFs) has gathered significant interest because of its prominent potential in many applications such as moisture harvesting, dehumidification, heat pump regulation, and hydrolysis catalysis. However, the reticular design and exploration of robust and high-performing Zr-MOFs for such purposes remains a sought-After endeavor. In this work, we present the deployment of reticular chemistry to target a series of robust Zr-MOFs based on a unique [2.2]paracyclophane (PCP) scaffold. The ease of functionalization of PCP enables the desired synthesis of three carboxylate linkers, one ditopic and two tetratopic, which further assemble into a total of five Zr-MOFs with distinct topological structures, i.e., a new 2D net (NU-700), fcu (NU-405), flu (NU-1800), she (NU-602), scu (NU-913). Notably, the water vapor sorption performances of all the Zr-MOFs are highly dependent on their framework topology and pore metric, in which NU-602 and NU-913 with uniform 1D channels exhibit S-shaped water sorption isotherms with a steep pore-filling step and high uptake capacities of 0.72 g g-1 at 70% relative humidity (RH) and 0.88 g g-1 at 60% RH, respectively. Moreover, NU-913 displays exceptionally high working capacity of 0.72 g g-1 in the range of 40-60% RH. Additionally, we demonstrate that the hydrolytic stability and water adsorption-desorption recyclability of NU-913 can be remarkably improved by capping the Zr6 nodes with the more hydrophobic agent, trifluoroacetic acid, making it a potential candidate for water sorption-based applications.
Regioselective Synthesis of 4,7,12,15-Tetrasubstituted [2.2]Paracyclophanes: A Modular Route Involving Optical Resolution
Biliz, Fatmanur,Cakici, Murat
supporting information, p. 4828 - 4834 (2021/09/20)
A practical synthetic method for preparing bis-(para)-pseudo-ortho and bis-(para)-pseudo-meta type 4,7,12,15-tetrasubstituted [2.2]paracyclophanes is reported. Regioselective double Rieche formylation was successfully applied to the corresponding dibromo[2.2]paracyclophanes under slightly modified conditions. Aldehydes reacted in an unknown direction with Rieche formylation agents, dichloromethyl methyl ether and titanium(IV) tetrachloride, leading to the formation of benzal chlorides. Formylated products were obtained after hydrolysis of these benzal chloride derivatives. Optical resolution was performed with the diastereomer method and (RP)-4,12-dibromo-7,15-diformyl[2.2]paracyclophane was successfully obtained in an enantiomerically pure form (99 % ee). Their synthetic utility is demonstrated with some exploratory transformations to access corresponding differently functionalized tetrasubstituted [2.2]paracyclophane derivatives.
Metal-to-Metal Distance Modulated Au(I)/Ru(II) Cyclophanyl Complexes: Cooperative Effects in Photoredox Catalysis
Bizzarri, Claudia,Br?se, Stefan,Diller, Rolf,Hassan, Zahid,Israil, Roumany,Kappes, Manfred M.,Nieger, Martin,Riehn, Christoph,Schüssler, Lars,Schneider, Erik K.,Weis, Patrick,Zippel, Christoph
supporting information, p. 15187 - 15200 (2021/11/01)
The modular synthesis of Au(I)/Ru(II) decorated mono- and heterobimetallic complexes with π-conjugated [2.2]paracyclophane is described. [2.2]Paracyclophane serves as a rigid spacer which holds the metal centers in precise spatial orientations and allows
A two-year water-stable 2D MOF with aqueous NIR photothermal conversion ability
Xue, Xiang,Wang, Jinghang,Zhu, Qinyi,Xue, Yu,Liu, Hewen
, p. 1374 - 1383 (2021/02/09)
Structural lability in humid air or water severely limits the practical use of MOFs. Developing new MOFs with exceptional water stability is interesting for both industrial applications and academic research. Herein we report a new method to improve the water stability of MOFs by using three-dimensional rigid shielding ligands. A very highly stable two-dimensional MOF (CuCP-MOF) is synthesized in this work, in which [2,2]paracyclophane dicarboxylate ligands are coordinated with Cu(ii) ions to form a paddle wheel structure. CuCP-MOF is a triclinic crystal with unit cell parametersa= 10.065 ?,b= 10.897 ?,c= 10.940 ?,α= 90.676°,β= 91.729°, andγ= 92.725° determined by single crystal X-ray diffraction and DFT simulation. It can easily form MOF nanosheets due to the large interlayer distance and weak interlayer interactions. It shows good aqueous stability, and remains intact after storage in water for two years, as evidenced by FTIR and XRD analyses. CuCP-MOF shows a strong absorption in the NIR range due to the d-d transition of Cu(ii). The aqueous dispersions of CuCP-MOF exhibit high NIR photothermal conversion efficiency, about 17.5% for a laser with an energy density of 5 W cm?2(808 nm) and 22.0% for a laser of 2 W cm?2on average.
Influencing the Self-Sorting Behavior of [2.2]Paracyclophane-Based Ligands by Introducing Isostructural Binding Motifs
Bohle, Fabian,Grimme, Stefan,Lützen, Arne,Rissanen, Kari,Schnakenburg, Gregor,Schneider, Andreas,Struch, Niklas,Topi?, Filip,Volbach, Lucia
, (2020/02/26)
Two isostructural ligands with either nitrile (Lnit) or isonitrile (Liso) moieties directly connected to a [2.2]paracyclophane backbone with pseudo-meta substitution pattern have been synthesized. The ligand itself (Lnit) or its precursors (Liso) were resolved by HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum-chemical simulated and experimental electronic circular dichroism (ECD) spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf)2] differ in their composition: whereas Lnit forms dinuclear complexes, Liso exclusively forms trinuclear ones. Furthermore, they also differ in their chiral self-sorting behavior as (rac)-Liso undergoes exclusive social self-sorting leading to a heterochiral assembly, whereas (rac)-Liso shows a twofold preference for the formation of homochiral complexes in a narcissistic self-sorting manner as proven by ESI mass spectrometry and NMR spectroscopy. Interestingly, upon crystallization, these discrete aggregates undergo structural transformation to coordination polymers, as evidenced by single-crystal X-ray diffraction.
Planar chiral [2.2]paracyclophane-based bisoxazoline ligands and their applications in Cu-Mediated N-H insertion reaction
Knoll, Daniel M.,Hu, Yuling,Hassan, Zahid,Nieger, Martin,Br?se, Stefan
supporting information, (2019/11/20)
New catalysts for important C-N bond formation are highly sought after. In this work, we demonstrate the synthesis and viability of a new class of planar chiral [2.2]paracyclophane-based bisoxazoline (BOX) ligands for the copper-catalyzed N-H insertion of α-diazocarbonyls into anilines. The reaction features a wide substrate scope and moderate to excellent yields, and delivers the valuable products at ambient conditions.
A highly stable, Au/Ru heterobimetallic photoredox catalyst with a [2.2]paracyclophane backbone
Knoll, Daniel M.,Zippel, Christoph,Hassan, Zahid,Nieger, Martin,Weis, Patrick,Kappes, Manfred M.,Br?se, Stefan
supporting information, p. 17704 - 17708 (2019/12/24)
We report the synthesis and catalytic application of a highly stable distance-defined Au/Ru heterobimetallic complex. [2.2]Paracyclophane serves as a backbone, holding the two metal centers in a spatial orientation and metal-metal fixed distance. The Au/Ru heterobimetallic complex is highly stable, easily accessible and exhibits promising catalytic activity in a visible-light mediated dual Au/Ru Meyer-Schuster rearrangement.
Chiroptical properties of oligophenylenes anchoring with stereogenic [2.2]paracyclophane
Ishioka, Sumire,Hasegawa, Masashi,Hara, Nobuyuki,Sasaki, Hiroaki,Nojima, Yuki,Imai, Yoshitane,Mazaki, Yasuhiro
supporting information, p. 640 - 643 (2019/07/12)
To elucidate the effect of π-conjugation length on chiroptical properties in circular dichroism (CD) and circularly polarized luminescence (CPL) spectra, stereogenic oligophenylenes containing biphenyl and terphenyl units linked by a planar chiral [2.2]paracyclophane were synthesized. Both compounds are highly emissive, and their chiroptical responses depend on the conjugation length. However, extended π-conjugation exhibited smaller dissymmetry factor (g-value) both in absorption and emission spectra.
Synthesis and chiroptical properties of stereogenic cyclic dimers based on 2,2′-biselenophene and [2.2]paracyclophane
Hasegawa, Masashi,Kobayakawa, Kosuke,Nojima, Yuki,Mazaki, Yasuhiro
supporting information, p. 8822 - 8826 (2019/10/22)
Stereogenic cyclic dimers based on 2,2′-biselenophene linked with [2.2]paracyclophane have been synthesized to investigate their chiroptical properties. Embedding selenophene led to the formation of intramolecular Se?π interactions between the two biselenophene strands. The resulting rigid cyclic system exhibits enhanced chiroptical properties when compared with its precursor. In addition, the electrochemical properties were also investigated.
Through-space π-delocalization in a conjugated macrocycle consisting of [2.2]paracyclophane
Wu, Yayu,Zhuang, Guilin,Cui, Shengsheng,Zhou, Yu,Wang, Jinyi,Huang, Qiang,Du, Pingwu
supporting information, p. 14617 - 14620 (2019/12/11)
Herein, we report the synthesis and characterization of a [2.2]paracyclophane-containing macrocycle (PCMC) as a new through-space conjugated macrocycle using only benzene groups as the skeleton. For comparison, a diphenylmethane-containing nanohoop macrocycle (DCMC) with a non-conjugated linker was also synthesized. Their structures were confirmed by NMR and HR-MS, and their photophysical properties were studied by UV-vis and fluorescence spectroscopies combined with theoretical calculations. The strain energy of PCMC was estimated to be as high as 72.58 kcal mol-1.
