title: Versatile syntheses of hemi-cryptophanes and a metallo-cryptophane from a hexa-functionalized C3v -symmetrical tribenzotriquinacene (TBTQ) derivative.
abstract: A number of three-fold C3v -symmetrical tribenzotriquinacene (TBTQ) cavitands were synthesized by a "metamorphosis-to-half" strategy, employing six-fold etherification reactions between the hexakis(chloromethyl)-TBTQ intermediate 2 a and various 5-functionalized resorcinols. X-ray structure analyses of single crystals of the cavitands revealed limited rotational flexibility of the resorcinol bridging units, which enables an apical, nearly co-axial orientation of the three functional groups and, as a consequence, the construction of nanoscale cage-like molecules via covalent or coordination bonding. On this basis, two TBTQ-based hemicryptophanes were prepared from the TBTQ cavitands via covalent bond formation in good yields. A dumbbell-shaped TBTQ-based metallo-cryptophane was also synthesized in 34 % yield by a solvothermal reaction between cadmium nitrate and two equivalents of the TBTQ-cavitand triacid, as confirmed by single-crystal X-ray diffraction and MALDI-ToF mass spectrometry.
authors: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000 (P.R. China).
authors: Jun
authors: J
authors: Wei
authors: Zhi-Min
authors: ZM
authors: Li
authors: Xiao-Jie
authors: XJ
authors: Jin
authors: Xiao-Jun
authors: XJ
authors: Yao
authors: Xiao-Ping
authors: XP
authors: Cao
authors: Hak-Fun
authors: HF
authors: Chow
authors: Dietmar
authors: D
authors: Kuck
mesh_terms: D001952:Bridged-Ring Compounds / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004988:Ethers, Cyclic / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D001952:Bridged-Ring Compounds; D004988:Ethers, Cyclic; D009942:Organometallic Compounds; D011083:Polycyclic Compounds; C523242:cryptophane
keywords: cage compounds; cavitands; hemicryptophane; metallo-cryptophane; tribenzotriquinacene