Steric Control of Photocatalytic Electron Transfer: A Predictive Framework Using Sterimol Parameters
- 1Department of Chemistry and Biochemistry University of South Carolina Columbia South Carolina USA
Abstract
Steric effects strongly influence excited‐state electron transfer, yet accurately predicting their impact remains challenging. In this study, we quantified the steric bulk of 11 axial substituents on a silicon phthalocyanine photocatalyst using Sterimol parameters, and fluorescence‐quenching experiments were performed with N,N‐diisopropylethylamine to evaluate the influence of steric effects on electron‐transfer efficiency. Multiparameter linear regression analysis revealed a correlation between the Sterimol parameters and the Stern–Volmer quenching constant (K SV), with distinct contributions from the Sterimol descriptors wB1, wB5, and wL. Among these descriptors, the minimum substituent width (wB1) was identified as the dominant steric parameter. Leave‐two‐out cross‐validation demonstrated reasonable predictive performance within the branching catalyst subset, highlighting the potential of this Sterimol‐based model to estimate K SV values for new structurally related silicon phthalocyanine photocatalysts. This work serves as a proof‐of‐concept for using Sterimol parameters to quantify steric effects in photocatalyst quenching and establish predictive structure–property relationships that may be extended to other photocatalyst classes.
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BibTeX
@article{harrison2026steric,
title = {{Steric Control of Photocatalytic Electron Transfer: A Predictive Framework Using Sterimol Parameters}},
author = {Christian J. Harrison and D. M. S. C. Dissanayake and Nicole M. Snyder and Alberto Smith and Grace Greway and Vitaly Rassolov and Aaron K. Vannucci and Sheryl L. Wiskur},
journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = aug,
doi = {10.1002/chem.71562},
url = {https://doi.org/10.1002/chem.71562},
note = {CC BY-NC 4.0},
}
RIS
TY - JOUR
TI - Steric Control of Photocatalytic Electron Transfer: A Predictive Framework Using Sterimol Parameters
AU - Christian J. Harrison
AU - D. M. S. C. Dissanayake
AU - Nicole M. Snyder
AU - Alberto Smith
AU - Grace Greway
AU - Vitaly Rassolov
AU - Aaron K. Vannucci
AU - Sheryl L. Wiskur
PY - 2026
DA - 2026/08/13
JO - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/chem.71562
UR - https://doi.org/10.1002/chem.71562
AB - Steric effects strongly influence excited‐state electron transfer, yet accurately predicting their impact remains challenging. In this study, we quantified the steric bulk of 11 axial substituents on a silicon phthalocyanine photocatalyst using Sterimol parameters, and fluorescence‐quenching experiments were performed with N,N‐diisopropylethylamine to evaluate the influence of steric effects on electron‐transfer efficiency. Multiparameter linear regression analysis revealed a correlation between the Sterimol parameters and the Stern–Volmer quenching constant (K SV), with distinct contributions from the Sterimol descriptors wB1, wB5, and wL. Among these descriptors, the minimum substituent width (wB1) was identified as the dominant steric parameter. Leave‐two‐out cross‐validation demonstrated reasonable predictive performance within the branching catalyst subset, highlighting the potential of this Sterimol‐based model to estimate K SV values for new structurally related silicon phthalocyanine photocatalysts. This work serves as a proof‐of‐concept for using Sterimol parameters to quantify steric effects in photocatalyst quenching and establish predictive structure–property relationships that may be extended to other photocatalyst classes.
SN - 0947-6539
SN - 1521-3765
ER -