LAUSR

Typically, conventional structure transitions occur from a low symmetry state to a higher symmetry state upon warming. In this work, an unexpected local symmetry breaking in the tetragonal diamondoid compound AgGaTe2 is reported, which, upon warming, evolves continuously from an undistorted ground state to a locally distorted state while retaining average crystallographic symmetry. This is a rare phenomenon previously referred to as emphanisis. This distorted state, caused by the weak sd3 orbital hybridization of tetrahedral Ag atoms, causes their displacement off the tetrahedron center and promotes a global distortion of the crystal structure resulting in strong acoustic–optical phonon scattering and an ultralow lattice thermal conductivity of 0.26 W m−1 K−1 at 850 K in AgGaTe2. The findings explain the underlying reason for the unexpectedly low thermal conductivities of silver‐based compounds compared to copper‐based analogs and provide a guideline to suppressing heat transport in diamondoid and other materials.