A Semiconductor or A One‐Dimensional Metal and Superconductor through Tellurium π Stacking

One-dimensional conductor: Strong π interactions between ecliptically stacked tellurium squares in Te4[Bi0.74Cl4] trigger excellent one-dimensional metallic conductivity as well as superconductivity below 7.15 K under ambient pressure. The electron-precise counterpart, Te4[Bi0.67Cl4], is a semiconductor. The bismuth content and temperature- dependent competition of intra- and inter-ring bonding account for the electronic conduction.