Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Hammett neural networks: prediction of frontier orbital energies of tungsten–benzylidyne photoredox complexes

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c9sc02339a· OSTI ID:1577578
 [1];  [1];  [1]
  1. Yale Univ., New Haven, CT (United States)
+ Show Author Affiliations
The successful application of Hammett parameters as input features for regressive machine learning models is demonstrated and applied to predict energies of frontier orbitals of highly reducing tungsten–benzylidyne complexes of the form W($$\equiv$$]CArR)L4X. Using a reference molecular framework and the meta- and para-substituent Hammett parameters of the ligands, the models predict energies of frontier orbitals that correlate with redox potentials. The regressive models capture the multivariate character of electron-donating trends as influenced by multiple substituents even for non-aryl ligands, harnessing the breadth of Hammett parameters in a generalized model. We find a tungsten catalyst with tetramethylethylenediamine (tmeda) equatorial ligands and axial methoxyl substituents that should attract significant experimental interest since it is predicted to be highly reducing when photoactivated with visible light. The utilization of Hammett parameters in this study presents a generalizable and compact representation for exploring the effects of ligand substitutions.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC)
OSTI ID:
1577578
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 28 Vol. 10; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (52)

Reactions of Sulphate Radicals with Substituted Pyridines: A Structure–Reactivity Correlation Analysis journal December 2007
Solvent dependence of the one-electron reduction of substituted benzo- and naphthoquinones journal May 1997
Predictive Models for HOMO and LUMO Energies of N-Donor Heterocycles as Ligands for Lanthanides Separation journal July 2018
Tuning metalloporphyrin and metallophthalocyanine redox potentials using ligand electrochemical (EL) and Hammett (σp) parametrization☆ journal June 2001
Tetracarbonylmolybdenum complexes of 2-(phenylhydrazino)pyridine ligands. journal February 2003
Electronic spectroscopy and photophysics of metal–alkylidyne complexes journal July 2005
The rise of deep learning in drug discovery journal June 2018
Materials discovery and design using machine learning journal September 2017
Machine Learning Methods to Predict Density Functional Theory B3LYP Energies of HOMO and LUMO Orbitals journal December 2016
Machine Learning Force Field Parameters from Ab Initio Data journal August 2017
Transferability in Machine Learning for Electronic Structure via the Molecular Orbital Basis journal July 2018
Accelerating Chemical Discovery with Machine Learning: Simulated Evolution of Spin Crossover Complexes with an Artificial Neural Network journal February 2018
ADMET Evaluation in Drug Discovery. Part 17: Development of Quantitative and Qualitative Prediction Models for Chemical-Induced Respiratory Toxicity journal May 2017
Thermodynamic and Structural Factors That Influence the Redox Potentials of Tungsten–Alkylidyne Complexes journal August 2017
Neural Networks for the Prediction of Organic Chemistry Reactions journal October 2016
A survey of Hammett substituent constants and resonance and field parameters journal March 1991
A Reëxamination of the Hammett Equation. journal October 1953
Assessment and Validation of Machine Learning Methods for Predicting Molecular Atomization Energies journal July 2013
Substituent constant correlations as predictors of spectroscopic, electrochemical, and photophysical properties in ring-substituted 2,2'-bipyridine complexes of rhenium(I) journal March 1992
Ground-State and Excited-State Structures of Tungsten–Benzylidyne Complexes journal February 2012
Oxidation-Potential Tuning of Tungsten–Alkylidyne Complexes over a 2 V Range journal July 2013
The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives journal January 1937
Inverse Design and Synthesis of acac-Coumarin Anchors for Robust TiO 2 Sensitization journal June 2011
Substituent Effects on Cobalt Diglyoxime Catalysts for Hydrogen Evolution journal November 2011
Improving the Accuracy of Density-Functional Theory Calculation:  The Statistical Correction Approach journal October 2004
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Bypassing the Kohn-Sham equations with machine learning journal October 2017
Friendship stability in adolescence is associated with ventral striatum responses to vicarious rewards journal January 2021
Skillful statistical models to predict seasonal wind speed and solar radiation in a Yangtze River estuary case study journal May 2020
Structure–property relationships based on Hammett constants in cyclometalated iridium( iii ) complexes: their application to the design of a fluorine-free FIrPic-like emitter journal January 2014
ANI-1: an extensible neural network potential with DFT accuracy at force field computational cost journal January 2017
Predictive and mechanistic multivariate linear regression models for reaction development journal January 2018
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Accurate Coulomb-fitting basis sets for H to Rn journal January 2006
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections journal January 2008
Neural network approach to quantum-chemistry data: Accurate prediction of density functional theory energies journal August 2009
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Machine learning of molecular electronic properties in chemical compound space journal September 2013
Fast and Accurate Modeling of Molecular Atomization Energies with Machine Learning journal January 2012
A new look at the statistical model identification journal December 1974
The Many Roles of Computation in Drug Discovery journal March 2004
Avogadro: an advanced semantic chemical editor, visualization, and analysis platform journal August 2012
Estimating the Dimension of a Model journal March 1978
The Effect of Substituents on the Half-Wave Potential of the Polarographic Reduction of Pyridine N -Oxide Derivatives journal October 1966
ANI-1: an extensible neural network potential with DFT accuracy at force field computational cost text January 2017
Machine learning of molecular electronic properties in chemical compound space text January 2013
Fast and Accurate Modeling of Molecular Atomization Energies with Machine Learning text January 2011
Neural networks for the prediction organic chemistry reactions text January 2016
By-passing the Kohn-Sham equations with machine learning text January 2016
Transferability in Machine Learning for Electronic Structure via the Molecular Orbital Basis text January 2018
Fast and accurate modeling of molecular atomization energies with machine learning text January 2012
Machine learning of molecular electronic properties in chemical compound space text January 2013

Similar Records

Quantitative Determination of Electronic Effects in Free Radicals through Open-Shell Hammett Substituent Constants
Journal Article · Thu Jun 12 20:00:00 EDT 2025 · Journal of the American Chemical Society · OSTI ID:2570127
Correlation between stabilities of uranyl ion complexes with various monocarboxylic acids and Hammett-Taft substituent constants
Journal Article · Wed Dec 31 23:00:00 EST 1986 · Sov. Radiochem. (Engl. Transl.); (United States) · OSTI ID:7200983
Inductive, steric, and environmental effects in the nonaqueous electrochemistry of hexakis(aryl isocyanide)chromium complexes
Journal Article · Wed Sep 01 00:00:00 EDT 1982 · Inorg. Chem.; (United States) · OSTI ID:6107722

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry