I am working on this low poly guy and created vertex groups to make it easier to assign materials. For some reason when I add new materials they are automatically assigned to the whole character then to the eye area, but not to any vertex group I have created or previously selected. I have tried deleting the materials that were automatically assigned but when I do that the material bellow that was lower in the node order now becomes assigned to those areas of the mesh. There is no material in the blend file however if you add two materials and adjust the color and you will see the issue. Its not the specific material but how blender is assigning them.