skip to main content

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 11:00 PM ET on Thursday, February 13 until 2:00 AM ET on Friday, February 14 due to maintenance. We apologize for the inconvenience.


This content will become publicly available on July 22, 2025

Title: Synthesis, Structures, and Magnetic Investigations of Nickel Phosphates: Ni 2 (PO 4 )(OH), Ni 7 (PO 4 ) 3 (HPO 4 )(OH) 3 , and NaNiPO 4 Including Potential Haldane Behavior
Award ID(s):
2219129
PAR ID:
10553693
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
Inorganic Chemistry
Volume:
63
Issue:
29
ISSN:
0020-1669
Page Range / eLocation ID:
13265 to 13277
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
  2. Abstract

    Addition of sub‐stoichiometric quantities of PEt3and diphenyl disulfide to a solution of [Ni(1,5‐cod)2] generates a mixture of [Ni3(SPh)4(PEt3)3] (1), unreacted [Ni(1,5‐cod)2], and [(1,5‐cod)Ni(PEt3)2], according to1H and31P{1H} NMR spectroscopic monitoring of the in situ reaction mixture. On standing, complex1converts into [Ni4(S)(Ph)(SPh)3(PEt3)3] (2), via formal addition of a “Ni(0)” equivalent, coupled with a CS oxidative addition step, which simultaneously generates the Ni‐bound phenyl ligand and the μ3‐sulfide ligand. Upon gentle heating, complex2converts into a mixture of [Ni5(S)2(SPh)2(PEt3)5] (3) and [Ni8(S)5(PEt3)7] (4), via further addition of “Ni(0)” equivalents, in combination with a series of C–S oxidative addition and CC reductive elimination steps, which serve to convert thiophenolate ligands into sulfide ligands and biphenyl. The presence of14in the reaction mixture is confirmed by their independent syntheses and subsequent spectroscopic characterization. Overall, this work provides an unprecedented level of detail of the early stages of Ni nanocluster growth and highlights the fundamental reaction steps (i.e., metal atom addition, CS oxidative addition, and CC reductive elimination) that are required to grow an individual cluster.

     
    more » « less
  3. Abstract

    A non‐aqueous proton electrolyte is devised by dissolving H3PO4into acetonitrile. The electrolyte exhibits unique vibrational signatures from stimulated Raman spectroscopy. Such an electrolyte exhibits unique characteristics compared to aqueous acidic electrolytes: 1) higher (de)protonation potential for a lower desolvation energy of protons, 2) better cycling stability by dissolution suppression, and 3) higher Coulombic efficiency owing to the lack of oxygen evolution reaction. Two non‐aqueous proton full cells exhibit better cycling stability, higher Coulombic efficiency, and less self‐discharge compared to the aqueous counterpart.

     
    more » « less
  4. Abstract

    A non‐aqueous proton electrolyte is devised by dissolving H3PO4into acetonitrile. The electrolyte exhibits unique vibrational signatures from stimulated Raman spectroscopy. Such an electrolyte exhibits unique characteristics compared to aqueous acidic electrolytes: 1) higher (de)protonation potential for a lower desolvation energy of protons, 2) better cycling stability by dissolution suppression, and 3) higher Coulombic efficiency owing to the lack of oxygen evolution reaction. Two non‐aqueous proton full cells exhibit better cycling stability, higher Coulombic efficiency, and less self‐discharge compared to the aqueous counterpart.

     
    more » « less