For the benefit of list, I've decided to work-around the problem using:

imapc_ssl_verify = no

Obviously I still welcome suggestions as to how I can get dsync working with 
Let's Encrypt certificates and when OpenSSL validates "ok" but Dovecot does not 
(despite Dovecot supposedly falling-back to OpenSSL).

For the record, I have done this sort of dsync before (i.e. "dsync backup" from 
source that has Let's Encrypt cert), I've never had a problem before, so I'm 
wondering if it's something peculiar to Dovecot 2.3.17.1 (whether a bug or a 
feature, it would be nice to know what's changed since I would have thought 
this sort of scenario should work "out of the box").

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