Hey neil - I cant find the option youre referring to but nothing has changed (by my hand at least) in a looong time. Since i set up multiplicity when i purchased it. Apart from the saga with wake-on-lan way back when, its been entirely uneventful.
Im inclined to think its some windows update or multiplicity update or driver/network update thats causing the detection of the pc to be delayed.
after more and more restarting to try and eliminate variables, it looks like its also not simply opening the gui which "fixes" it. That was just luck/a fluke.
After a restart of the secondary, cant mouse over, tray icon is grayed out like its not detecting a connection, yet gui shows the pc as being on/there.

clicking its gear icon as sean alluded to earlier also shows

yet the tray icon remains gray and seamless remains down. After some arbitrary amount of time (or some mucking around clicking on things in the gui like the former image to test connection) it lights up. It used to be all but instant. the pc was able to restart and i'd mouse over and log in. I just waited 4 minutes and it finally detected the other pc on its own.
also saw the "flush dns cache" option in the tray after right clicking. hit it on both pc's. no change.
On the one hand, at least it still works at some point, whether it be alah waiting around (no fun when youre working) or mashing buttons in the gui to force it to try and update/see the secondary faster (cumbersome) it does still work eventually. Tarnishing the experience to no small degree - but at least not a full/dead stop.
to be fair, most of the time the pc just sleeps anyhow. when its woken it connects instantly no problamo. its purely the restarts.