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Hi,
We're sorry about the trouble. You can try using the Creative Cloud cleaner tool to remove Photoshop CS6 prior to installing the latest version when you purchase the subscription. You can check out the steps to use the Creative Cloud cleaner tool here: https://helpx.adobe.com/creative-cloud/kb/cc-cleaner-tool-installation-problems.html
Let us know if it helps!
Regards,
Nikunj
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Here's why: the uninstaller has 32-bit components, which is not allowed in Big Sur. So it won't launch.