Patching Crypt::SSLeay should not help because Net::SMTP::TLS uses IO::Socket::SSL which uses Net::SSLeay and not Crypt::SSLeay. But contrary to your description your change applies to IO::Socket::SSL and not Crypt::SSLeay, so it works a bit even if the general approach is wrong. The real problem is that Net::SMTP::TLS uses SSL_version in a wrong and never documented way and thus broke once the version check was done more strict (and the intended version string never did what the author tried to do). The problem you run into is known for several years (rt#77400) but the package is not changed since 2006 so it will probably never be fixed.
I would recommend you to just use Net::SSLGlue::SMTP, which patches the core module Net::SMTP to provide TLS support. You'll probably need to specify a SSL_ca_file or SSL_ca_path to specify where your CA are, or if you don't care at all about security you could set SSL_verify_mode to 0 (but in this case you should ask yourself why you use TLS at all).
In reply to Re: Couldn't start TLS: SSL connect attempt failed with unknown error error:14090086:SSL routines:SSL3_GET_SERVER_CERTIFICATE:certificate verify failed
by noxxi
in thread Couldn't start TLS: SSL connect attempt failed with unknown error error:14090086:SSL routines:SSL3_GET_SERVER_CERTIFICATE:certificate verify failed
by rich101v2
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