are you manually overclocking your GPU card?
If the Hot Spot goes above 110c it is overheating and throttling.
If you reset everything back to "Default" in Radeon Settings are you still getting those high temperature?
Because the image you showed you have "Custom" settings enabled.
First: I would first check to make sure you have good air flow inside your PC by removing the side panel and see if the GPU runs cooler. Same with the CPU temperatures.
If it does then you have poor air circulation inside your PC.
Second: I would check to make sure the GPU Heat Sink and fan is clean and the air flow is not obstructed.
Third: Make sure you fans are running at Maximum when it gets at or above 80c. Try to create an aggressive Fan Profile where the fans turn on at a lower temperature and and goes to maximum at a lower temperature.
Fourth: if it continues to go above 100c I would consider to change the Thermal paste if it doesn't void your Warranty otherwise I would suggest to open a Warranty ticket to have them check out the GPU card.
NOTE: Just learned that if the GPU Hot Spot goes to 118c the GPU card will shut down.