196316-30-0Relevant articles and documents
Improved synthesis of (±)-4,12-dihydroxy[2.2]paracyclophane and Its enantiomeric resolution by enzymatic methods: Planar chiral (R)- and (S)-phanol
Braddock, D. Christopher,MacGilp, Iain D.,Perry, Benjamin G.
, p. 8679 - 8681 (2002)
(±)-4,12-Dihydroxy[2.2]paracyclophane [(±)-PHANOL] is readily prepared from [2.2]paracyclophane by an improved synthetic protocol. Enzymatic kinetic resolution of its bis-acetate proceeds with good enantioselection. Separation, hydrolysis, and recrystallization provides both enantiomers of PHANOL in high enantiopurity.
Chiroptical properties of oligophenylenes anchoring with stereogenic [2.2]paracyclophane
Ishioka, Sumire,Hasegawa, Masashi,Hara, Nobuyuki,Sasaki, Hiroaki,Nojima, Yuki,Imai, Yoshitane,Mazaki, Yasuhiro
, p. 640 - 643 (2019)
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 of novel alternating π-conjugated copolymers having [2.2]paracyclophane and fluorene units in the main chain leading to the blue light-emitting materials
Morisaki, Yasuhiro,Chujo, Yoshiki
, p. 194 - 195 (2002)
Novel through-space π-conjugated polymers having [2.2]paracyclophane and fluorene units were synthesized by Heck-Sonogashira coupling reaction. The polymers exhibited strong blue fluorescence in solution and in the solid state.
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)
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.
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
, p. 8822 - 8826 (2019)
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.
Regioselective Synthesis of 4,7,12,15-Tetrasubstituted [2.2]Paracyclophanes: A Modular Route Involving Optical Resolution
Biliz, Fatmanur,Cakici, Murat
, p. 4828 - 4834 (2021)
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.
Synthesis, chiral resolution, and absolute configuration of dissymmetric 4,15-difunctionalized [2.2]paracyclophanes
Meyer-Eppler, Georg,Sure, Rebecca,Schneider, Andreas,Schnakenburg, Gregor,Grimme, Stefan,Lützen, Arne
, p. 6679 - 6687 (2014)
Despite the fact that functionalized planar chiral [2.2]paracyclophanes have received a lot of attention, the chemistry of pseudo-meta 4,15-distubstituted [2.2]paracyclophanes is largely unexplored. This is mainly due to the fact that the 4,5-dibromo-functionalized [2.2]paracyclophane is much less prone to halogen-metal exchange reactions than its constitutional pseudo-ortho or pseudo-para isomers. Here, we give an account of an efficient protocol to achieve this, which allows the synthesis of a broad variety of 4,15-disubstituted [2.2]paracyclophanes. Furthermore, we were able to resolve several of the racemic compounds via chiral HPLC and assign the absolute configurations of the isolated enantiomers by X-ray diffraction and/or by the comparison of calculated and measured CD-spectra.
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
