title: Phosphorescent Decanuclear Bimetallic Pt6M4(M = Zn, Fe) Tetrahedral Cages.
abstract: Coordination-driven self-assembly delivers discrete, nanoscopic architectures that may preserve or enhance the physicochemical properties of their parent building blocks. Herein, we report the syntheses, characterization, and photophysical properties of two tetrahedral cages, [ZnII4L6](PF6)8(C1) and [FeII4L6](OTf)8(C2), where L = PtII(PEt3)2(C≡C-bpy)2(PEt3= triethylphosphine; C≡C-bpy = 5-ethynyl-2,2'-bipyridine) and OTf = trifluoromethanesulfonate. C1 and C2 were assembled in isolated yields of 72% and 81% by treating 2 equiv of Zn(NO3)2·6H2O or Fe(OTf)2with 3 equiv of L, respectively. Both cages were fully characterized by NMR, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction (SCXRD). The local D3symmetry at each polypyridyl metal node raises the possibility of a number of isomeric cages; however, only the homochiral enantiomers (ΔΔΔΔ and ΛΛΛΛ) are formed based on1H NMR and SCXRD. C1 exhibits phosphorescence centered at 545 nm with a quantum yield of 10% in N2-degassed acetonitrile at 25 °C. The quantum yield of C2 is significantly lower due to a nonradiative relaxation from5MC (MC = metal-centered) states introduced by the FeIInodes.
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York , Buffalo, New York 14260, United States.
authors.forename: Yuzhen
authors.identifier: http://orcid.org/0000-0003-2763-9798
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York , Buffalo, New York 14260, United States.
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Crawley
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York , Buffalo, New York 14260, United States.
authors.forename: Cory E
authors.initials: CE
authors.lastname: Hauke
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York , Buffalo, New York 14260, United States.
authors.forename: Alan E
authors.initials: AE
authors.lastname: Friedman
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York , Buffalo, New York 14260, United States.
authors.forename: Timothy R
authors.identifier: http://orcid.org/0000-0002-7668-8089
authors.initials: TR
authors.lastname: Cook