skip to main content


Title: Structural and Mechanistic Differences in Mixed-Linker Zeolitic Imidazolate Framework Synthesis by Solvent Assisted Linker Exchange and de Novo Routes
Award ID(s):
1264874
NSF-PAR ID:
10026090
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
139
Issue:
16
ISSN:
0002-7863
Page Range / eLocation ID:
5906 to 5915
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Sulfur K-edge XAS data provide a unique tool to examine oxidation states and covalency in electronically complex S-based ligands. We present sulfur K-edge X-ray absorption spectroscopy on a discrete redox-series of Ni-based tetrathiafulvalene tetrathiolate (TTFtt) complexes as well as on a 1D coordination polymer (CP), NiTTFtt. Experiment and theory suggest that Ni–S covalency decreases with oxidation which has implications for charge transport pathways. 
    more » « less
  2. null (Ed.)
    A bidentate pyrazolylpyridine ligand (HL) was installed on divalent nickel to give [(HL) 2 Ni(NO 3 )]NO 3 . This compound reacts with a bis-silylated heterocycle, 1,4-bis-(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (TMS 2 Pz) to simultaneously reduce one of the nitrate ligands and deprotonate one of the HL ligands, giving octahedral (HL)(L − )Ni(NO 3 ). The mononitrate species formed is then further reacted with TMS 2 Pz to doubly deoxygenate nitrate and form [(L − )Ni(NO)] 2 , dimeric via bridging pyrazolate with bent nitrosyl ligands, representing a two-electron reduction of coordinated nitrate. Independent synthesis of a dimeric species [(L − )Ni(Br)] 2 is reported and effectively assembles two metals with better atom economy. 
    more » « less
  3. null (Ed.)
    Here, we report the quantitative electroreduction of CO 2 to CO by a PNP-pincer iridium( i ) complex bearing amino linkers in DMF/water. The electrocatalytic properties greatly depend on the choice of linker within the ligand. The complex 3-N is far superior to the analogues with methylene and oxygen linkers, showing higher activity and better selectivity for CO 2 over proton reduction. 
    more » « less