Edit: Still trying to figure out why TG Pro shows that much higher temp, the istat menu doesn't seem to show that specific temp, it is not the same as the memory proximity 6 which is the DRAM. So still investigating!
Ok I think I figured it out. I am almost certain it is the TG Pro app that is giving the wrong reading. I just installed it, and my proximity sensor 6 also went over 100c.
I put it side by side to my istat reading, which is 40c and what I believe to be correct because there was no change in fan speeds or anything like that, or thermal throttling.
The TG Pro app has a bug, it can be common with new gpus for this to happen with monitoring software.
It is also possible that it can trigger higher fan speeds with the app if it's reading this incorrectly. I would uninstall it and use istat.
It doesn't make sense for one sensor to be so wildly differently, so I am 99% sure it's just a buggy app.
Here is a screen shot, side by side: