Electronic Effects in 1,3-diaryl-1,3-diketone Reduction Potentials Correlate with  0

The scarcity of nitrogen in Earth’s crust, combined with challenging synthesis, have made inorganic nitrides a relatively-unexplored class of compounds compared to their naturally-abundant oxide counterparts. To facilitate exploration of their compositional space via a priori modeling, and to help a posteriori structure verification not limited to inferring the oxidation state of redox-active cations, we derive a suite of bond-valence parameters and Lewis-acid strength values for 76 cations observed bonding to N3-, and further outline a baseline statistical knowledge of bond lengths for these compounds. We examine structural and electronic effects responsible for the functional properties and anomalous bonding behavior of inorganic nitrides, and identify promising venues for exploring uncharted compositional spaces beyond the reach of high-throughput computational methods. We find that many mechanisms of bond-length variation ubiquitous to oxide and oxysalt compounds (e.g., lone-pair stereoactivity, the Jahn-Teller and pseudo Jahn-Teller effects) are similarly pervasive in inorganic nitrides, and are occasionally observed to result in greater distortion magnitude than their oxide counterparts. We identify inorganic nitrides with multiply-bonded metal ions as a promising venue in heterogeneous catalysis, e.g. in the development of a post-Haber-Bosch process proceeding at milder reaction conditions, thus representing further opportunity in the thriving exploration of the functional properties of this emerging class of materials.

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Cobaloxime-Based Double Complex Salts as Efficient and Versatile Catalysts for the Light-Driven Hydrogen Evolution Reaction

10.26434/chemrxiv.11537661 ◽

2020 ◽

Author(s):

Elisabeth Hofmeister ◽

Jisoo Woo ◽

Tobias Ullrich ◽

Lydia Petermann ◽

Kevin Hanus ◽

...

Keyword(s):

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Systematic Study ◽

Cobalt Complexes ◽

Spectroscopic Studies ◽

Double Complex ◽

Double Complex Salts ◽

Noble Metal Catalysts ◽

Reduction Potentials ◽

Complex Salts

Cobaloximes and their BF2-bridged analogues have emerged as promising non-noble metal catalysts for the photocatalytic hydrogen evolution reaction (HER). Herein we report the serendipitous discovery that double complex salts such as [Co(dmgh)2py2]+[Co(dmgBPh2)2Cl2]- can be obtained in good yields by treatment of commercially available [Co(dmgh)2pyCl] with triarylboranes. A systematic study on the use of such double complex salts and their single salts with simple counterions as photocatalysts revealed HER activities comparable or superior to existing cobaloxime catalysts and suggests ample opportunities for this compound class in catalyst/photosensitizer dyads and immobilized architectures. Preliminary electrochemical and spectroscopic studies indicate that one key advantage of these charged cobalt complexes is that the reduction potentials as well as the electrostatic interaction with charged photosensitizers can be tuned.

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Phosphoryl- and Phosphonium-Bridged Viologens as Stable Two- and Three-Electron Acceptors for Organic Electrodes

10.26434/chemrxiv.12711770.v1 ◽

2020 ◽

Author(s):

Colin R. Bridges ◽

Andryj M. Borys ◽

Vanessa Béland ◽

Joshua R. Gaffen ◽

Thomas Baumgartner

Keyword(s):

Molecular Weight ◽

Organic Molecules ◽

Electrode Materials ◽

High Energy ◽

Electron Acceptors ◽

Low Molecular Weight ◽

Reduction Potentials ◽

Organic Electrode ◽

High Reduction ◽

High Specific Energy

Low molecular weight organic molecules that can accept multiple electrons at high reduction potentials are sought after as electrode materials for high-energy sustainable batteries. To date their synthesis has been difficult, and organic scaffolds for electron donors significantly outnumber electron acceptors. Herein, we report two highly electron deficient phosphaviologen derivatives from a phosphorus-bridged 4,4-bipyridine and characterize their electrochemical properties. Phosphaviologen sulfide (PVS) and P-methyl phosphaviologen (PVM) accept two and three electrons at high reduction potentials, respectively. PVM can reversibly accept 3 electrons between 3-3.6 V vs. Li/Li+ with an equivalent molecular weight of 102 g/(mol e-) (262 mAh/g), making it a promising scaffold for sustainable organic electrode materials having high specific energy densities.

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