Phosphorescent Decanuclear Bimetallic Pt6M4 (M = Zn, Fe) Tetrahedral Cages

Yuzhen Zhang; Matthew R. Crawley; Cory E. Hauke; Alan E. Friedman; Timothy R. Cook

doi:10.1021/acs.inorgchem.7b00501

Phosphorescent Decanuclear Bimetallic Pt₆M₄ (M = Zn, Fe) Tetrahedral Cages

Yuzhen Zhang
, Matthew R. Crawley
, Cory E. Hauke
, Alan E. Friedman
, Timothy R. Cook

SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

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, [Zn^II₄L₆](PF₆)₈ (C1) and [Fe^II₄L₆](OTf)₈ (C2), where L = Pt^II(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)₂ with 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 D₃ symmetry at each polypyridyl metal node raises the possibility of a number of isomeric cages; however, only the homochiral enantiomers (ΔΔΔΔ and λ λ λ λ) are formed based on ¹H 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 from ⁵MC (MC = metal-centered) states introduced by the Fe^II nodes.

Original language	English
Pages (from-to)	4258-4262
Number of pages	5
Journal	Inorganic Chemistry
Volume	56
Issue number	8
DOIs	https://doi.org/10.1021/acs.inorgchem.7b00501
State	Published - Apr 17 2017

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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)2 with 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 D3 symmetry at each polypyridyl metal node raises the possibility of a number of isomeric cages; however, only the homochiral enantiomers (ΔΔΔΔ and λ λ λ λ) are formed based on 1H 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 from 5MC (MC = metal-centered) states introduced by the FeII nodes.",

author = "Yuzhen Zhang and Crawley, \{Matthew R.\} and Hauke, \{Cory E.\} and Friedman, \{Alan E.\} and Cook, \{Timothy R.\}",

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AU - Zhang, Yuzhen

AU - Crawley, Matthew R.

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AU - Friedman, Alan E.

AU - Cook, Timothy R.

PY - 2017/4/17

Y1 - 2017/4/17

N2 - 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)2 with 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 D3 symmetry at each polypyridyl metal node raises the possibility of a number of isomeric cages; however, only the homochiral enantiomers (ΔΔΔΔ and λ λ λ λ) are formed based on 1H 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 from 5MC (MC = metal-centered) states introduced by the FeII nodes.

AB - 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)2 with 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 D3 symmetry at each polypyridyl metal node raises the possibility of a number of isomeric cages; however, only the homochiral enantiomers (ΔΔΔΔ and λ λ λ λ) are formed based on 1H 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 from 5MC (MC = metal-centered) states introduced by the FeII nodes.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

Phosphorescent Decanuclear Bimetallic Pt₆M₄ (M = Zn, Fe) Tetrahedral Cages

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