Per some previous reports, SMTP on Big Sur did not include support for TLSv1.3.
Per Apple, yes, current Mail app does include support for TLSv1.3:
iOS, iPadOS, and macOS support Transport Layer Security (TLS 1.0, TLS 1.1, TLS 1.2, TLS 1.3) and Datagram Transport Layer Security (DTLS). The TLS protocol supports both AES128 and AES256, and prefers cipher suites with forward secrecy. Internet apps such as Safari, Calendar, and Mail automatically use this protocol to enable an encrypted communication channel between the device and network services. High-level APIs (such as CFNetwork) make it easy for developers to adopt TLS in their apps, while low-level APIs (such as Network.framework) provide fine-grained control. CFNetwork disallows SSL 3, and apps that use WebKit (such as Safari) are prohibited from making an SSL 3 connection.
Also check whether the service requires an app-specific password:
Sign in to apps with your Apple ID using app-specific passwords - Apple Support
Consider an upgrade to Monterey or Ventura, if your Mac supports it.
How to download macOS - Apple Support
Pending newer macOS, the Thunderbird mail client app can likely connect as that includes its own TLS support.