One‐pot synthesis of [2+2]‐helicate‐like macrocycle and 2+4‐μ4‐oxo tetranuclear open frame complexes : Chiroptical properties and asymmetric oxidative coupling of 2‐naphthols
Chinnaraja, E., Arunachalam, R., Pillai, R. S., Peuronen, A., Rissanen, K., & Subramanian, P. S. (2020). One‐pot synthesis of [2+2]‐helicate‐like macrocycle and 2+4‐μ4‐oxo tetranuclear open frame complexes : Chiroptical properties and asymmetric oxidative coupling of 2‐naphthols. Applied Organometallic Chemistry, 34(8), Article e5666. https://doi.org/10.1002/aoc.5666
Published in
Applied Organometallic ChemistryAuthors
Date
2020Discipline
Epäorgaaninen ja analyyttinen kemiaOrgaaninen kemiaNanoscience CenterInorganic and Analytical ChemistryOrganic ChemistryNanoscience CenterCopyright
© 2020 John Wiley & Sons, Ltd.
Synthesis of binuclear Cu(II) terminally closed [2+2]‐ double‐stranded helicate‐like macrocycles 1, 1′,1″, 2, 2′, 2″ and 2+4‐μ4‐oxo tetranuclear open frame complexes 3, 3′, 3″, 4, 4′, 4″ are established. Adapting one‐pot self‐assembly technique from simple three components systems: 1,1′‐binaphthyl‐2,2′‐diamine, 4‐methyl‐2,6‐diformyl phenol and cupric salts, the helicate‐like [2+2]‐ macrocyclic complexes 1–1″, 2–2″ and 2+4‐μ4‐oxo tetranuclear complexes 3–3″, 4–4″ were obtained by appropriately altering the reaction condition such as temperature and subcomponent ratio. Density Functional Theory (DFT) calculations were carried out for understanding the structural geometries, intermediates involved in the diverse formation of [2+2] and 2+4 frameworks. The single crystal X‐ray structures obtained for 1′, 2 and 3 confirms the self‐assembly process in line with DFT. This detailed analysis tempted us to derive a plausible mechanism for this long standing challenge in the synthesis of such macrocycles using 1,1′‐binaphthyl‐2,2′‐diamine (BNDA) and aromatic aldehyde. The chiroptical properties of enantiopure complexes and their catalytic applications in asymmetric oxidative coupling of 2‐naphthol to chiral 1,1’‐Bi‐2‐naphthol (BINOL) achieved in good yield and ee were discussed.
...


Publisher
John Wiley & SonsISSN Search the Publication Forum
0268-2605Keywords
Publication in research information system
https://converis.jyu.fi/converis/portal/detail/Publication/35425301
Metadata
Show full item recordCollections
Related funder(s)
Academy of FinlandFunding program(s)
Academy Project, AoF
Additional information about funding
DST‐SERB Govt. of India; Academy of Finland. Grant Numbers: 277250, 315911; DST‐SERB New DelhiLicense
Related items
Showing items with similar title or keywords.
-
Tertiary Chiral Nanostructures from C‐H∙∙∙F Directed Assembly of Chiroptical Superatoms
Shen, Hui; Xu, Zhen; Wang, Lingzheng; Han, Ying-Zi; Liu, Xianhu; Malola, Sami; Teo, Boon K.; Häkkinen, Hannu; Zheng, Nanfeng (Wiley, 2021)Chiral hierarchical structures are universal in nature, whereas quite challenging to mimic in man-made synthesis. We report herein the synthesis and structure of tertiary chiral nanostructures with 100% optical purity. A ... -
Self-assembly of metallosupramolecular rhombi from chiral concave 9,9'-spirobifluorene-derived bis(pyridine) ligands
Hovorka, Rainer; Hytteballe, Sophie; Piehler, Torsten; Meyer-Eppler, Georg; Topic, Filip; Rissanen, Kari; Engeser, Marianne; Lützen, Arne (Beilstein - Institut zur Foerderung der Chemischen Wissenschaften, 2014)Two new 9,9’-spirobifluorene-based bis(4-pyridines) were synthesised in enantiopure and one also in racemic form. These ligands act as concave templates and form metallosupramolecular [(dppp)₂M₂L₂] rhombi with cis-protected ... -
Cation binding resorcinarene bis-crowns: the effect of lower rim alkyl chain length on crystal packing and solid lipid nanoparticles
Helttunen, Kaisa; Salorinne, Kirsi; Barboza, Tahnie; Barbosa, Hélène Campos; Suhonen, Aku; Nissinen, Maija (Centre National de la Recherche Scientifique and The Royal Society of Chemistry, 2012)A group of seven resorcinarene bis-crown ethers (CNBC5) with two polyether bridges at the upper rim and either propyl, butyl, pentyl, heptyl, nonyl, decyl or undecyl groups at the lower rim were synthesized and their binding ... -
Gelation and gel properties of two- and three-component pyrene based low molecular weight organogelators
Leivo, Kimmo (University of Jyväskylä, 2011)The research described in this thesis covers the synthesis, characterization and the study of the gelation ability of fteen pyrene based low molecular weight organogelators (LMOGs). The gelation and gel properties were ... -
Self-assembly of a M4L6 complex with unexpected S4 symmetry
Giri, Chandan; Topic, Filip; Mal, Prasenjit; Rissanen, Kari (R S C Publications, 2014)Using 1,4-diaminobenzene and 2-formylpyridine as simple building blocks results in a 1D ligand (rod, L2) to 2D (M4L4 grid, C1) to 3D (S4 symmetrical M4L6, C2) complexes upon sequential addition of Cu(I) and Fe(II) ...