If you wish to use TLS, or are using TLS authentication in a Office 365 Hybrid environment, and have manually changed or renewed the SSL certificate, you may still get errors about unable to initiate the TLS session (STARTTLS), even though the SSL certificate has been correctly renewed. Just setting the SSL certificate to be used with SMTP is not enough to make TLS work correctly. You also need to (re-)configure the TLS certificate name on your send and receive connectors.

As stated by the manual:

TlsCertificateName
The TlsCertificateName parameter specifies the X.509 certificate to use with TLS sessions and secure mail. Valid input for this parameter is [I]Issuer[S]Subject. The Issuer val  ...