Thermochromic luminescent compounds with d10 metal ions are interesting materials for applications such as sensors or display devices. However, these properties are difficult to predict prior to their synthesis. In this communication, we investigated materials with structural assemblies known to be responsible of distinct luminescence mechanisms and show that they can be interesting potential thermometers. Thus, we compared the synthesis of a zinc halide and a copper halide based compounds which only differ in their ability to create clusters with metallophilic interactions. The compounds synthesized by hydrothermal method have been structurally characterized by Single-crystal X-ray diffraction, Solid-State NMR, FTIR, UV-Visible spectroscopy, thermal analysis and EPR. The photoluminescence properties of the two materials have been characterized at different temperatures. The copper bromide compound shows luminescence thermochromism in a wide spectrum of colors owing to the formation of clusters generating multi-emission bands while the zinc bromide exhibits a single emission band and no thermochromism.