Then yes, if the IPv6 addresses on your PC are not from your routed /64 then you won't be making any IPv6 connections from them. At this point I'd suggest not worry about any sort of dynamic address assignment such as SLAAC or DHCPv6 and manually assign address just to make sure the "pipes" are working correctly. After that you can worry about dynamic assignment.
For all I know the firmware on your router might not even be able to help with SLAAC. I haven't worked with one of those routers, and I don't know it's interface, with GUI or CLI, so I can't tell you how to do things, only what needs to be accomplished.
I'm not sure what you were doing with forwarding or DMZ, but none of that is necessary for an HE tunnel. The HE traffic is passed through via Protocol 41 (not Port 41), and since it's a Protocol, not a Port, you can't even do forwarding of that traffic. There are some ISP's and routers that don't properly pass Protocol 41, and the only solution to that is generally to get different equipment or to get the ISP to life their blocks. Using a DMZ might be a jury rig to get things working, but I wouldn't suggest using it in the long run. Remember, enabling a DMZ, at least the way it's defined on most routers is functionally the same as disabling the "firewall" since it just passes all traffic through without examining it.
Based on the tunnel information you provided, your router will have two IPv6 address. The first is Client IPv6 Address:2001:470:a:524::2/64, that's the one used to establish your end of the tunnel, and what allows your router to communicate via IPv6 with the internet. The second one will be from your Routed /64:2001:470:b:524::/64. You could assign it as 2001:470:b:524::2 just to keep the machine address the same, with the only difference between the network portion of the address. That's how I simplify things for myself.
Then follow cholzhauer suggestions of running "netsh interface ipv6 reset" on your PC to reset all of the IPv6 settings back to default to start over. Finally assign your PC and address of 2001:470:b:524::100 with the gateway address being the routers fe80 address. (cholzhauer address suggestions would work as well, mine just come from my own personal style for doing things) After that you should be able to reach the internet via IPv6 from the PC.
One other piece of advice. Since this work is apparently being done as some sort of college assignment, get your professor involved. Let them look over what you've already done and critique it. Aside from being inexperienced, from some of your descriptions you seem to have done some decidedly odd things. I could tell far more (and recommend far more) from a 5 minute hands on look at your setup than I could tell you in days of back and forth on a message board. After all, that is one part of a college instructors job, to help their student and provide help and guidance. It's an invaluable resource, use it.