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I mean when I make the entry you suggested a:1:{i:0;s:9:"mysite.ca";} with phpMyAdmin, that is exactly what appears in the SMTP host(s)field under the Mail Setup Preferences in the site.
I was expecting to see just mysite.ca there, but I get the entire "a:1:{i:0;s:9:"mysite.ca";}"
Optimism is the mother of disappointment.