Steric Pruning Unlocks Hierarchical Structuring, Thermochromism, C‐H/O Activation, and 6‐electron Redox Transmetalation in Planar Bismuth Triamides

W William P. Howlett T Tyler J. Hannah (Department of Chemistry Dalhousie University 6243 Alumni Crescent Halifax NS B3H 4R2 Canada) L Lars J. C. van der Zee (Van ’t Hoff Institute for Molecular Sciences University of Amsterdam Amsterdam Netherlands) J J. Chris Slootweg (Van ’t Hoff Institute for Molecular Sciences University of Amsterdam Amsterdam Netherlands) J Jason D. Masuda (Department of Chemistry Saint Mary's University 923 Robie Street Halifax NS B3H 3C3 Canada) S Saurabh S. Chitnis (Department of Chemistry, Dalhousie University, 6243 Alumni Crescent, Halifax, Nova Scotia B3H 4R2, Canada)

Abstract

Abstract Planar bismuth triamides with tunable stereoelectronics offer a versatile platform for studying the effects of geometric constraints in p‐block elements. Here we show that exploring the low steric bulk regime in these compounds unlocks categorically new phenomena such as epitaxial hierarchical ordering, thermochromism, C─H/O activation, and 6‐electron pincer‐to‐pincer redox transmetalation. These behaviors are not observed in sterically encumbered derivatives, emphasizing the role of steric modulation in unlocking new phenomena in geometrically‐constrained main group complexes.

Article Details

Volume / Issue Vol. 65, Issue 1
Published January 02, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (6)

W

William P. Howlett

T

Tyler J. Hannah

Department of Chemistry Dalhousie University 6243 Alumni Crescent Halifax NS B3H 4R2 Canada

L

Lars J. C. van der Zee

Van ’t Hoff Institute for Molecular Sciences University of Amsterdam Amsterdam Netherlands

J

J. Chris Slootweg

Van ’t Hoff Institute for Molecular Sciences University of Amsterdam Amsterdam Netherlands

J

Jason D. Masuda

Department of Chemistry Saint Mary's University 923 Robie Street Halifax NS B3H 3C3 Canada

S

Saurabh S. Chitnis

Department of Chemistry, Dalhousie University, 6243 Alumni Crescent, Halifax, Nova Scotia B3H 4R2, Canada