A Dinuclear Metallobridged Super Aryl‐Extended Calix[4]pyrrole Cavitand. (30th March 2022)

• Record Type: Journal Article
• Authors: Sun, Qingqing; Escobar, Luis; Ballester, Pablo
• Is Part Of: Angewandte Chemie. Volume 134:Number 22(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-30
• Subjects: Host–Guest Systems -- Inclusion Compounds -- Metal Coordination -- Metallocavitands -- Molecular Containers; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202202140
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A super aryl‐extended calix[4]pyrrole equipped with four oxazolo[4, 5‐ b ]pyrazinyl units at its upper rim is reported. Its Pt II /Pd II ‐metallobridged cavitand counterparts were obtained by treatment with 2 equiv of cis ‐protected metal corners, [M(dppp)(OTf)2 ] (dppp=1, 3‐( bis ‐diphenylphosphino)propane). The metal corners arranged their axial phenyl substituents near the aromatic walls of the cavitand leading to the formation of inclusion complexes as single conformers. We characterized the inclusion complexes in solution using NMR spectroscopy. Selected complexes were also characterized in the gas‐phase and in the solid‐state using mass spectrometry and X‐ray diffraction analysis. The dimensions of the open portals of the dinuclear complexes were found to be dependent on the included guest. The results of DFT calculations served to explain the dissimilar complexation‐induced shifts observed in the dinuclear inclusion complexes with mono ‐ and bis ‐formamide guests. Abstract : Treating a super aryl‐extended calix[4]pyrrole with 2 equivalents of cis ‐protected [M(dppp)(OTf)2 ] as the metal corners (M=Pt, Pd; dppp=1, 3‐( bis ‐diphenylphosphino)propane) has led to the formation of a dinuclear metallobridged cavitand. Inclusion complexes of the metallocavitand are formed as single conformers and the dimensions of their open portals are dependent of the included guests.