PhotoStructure's library stores paths as URIs:
That way, if anything goes sideways, you haven't lost any of your files. One last, last thing: take a backup of all your stuff before you do anything, and, preferably, have it disconnected. It'll be a bit slower due to network latency and bandwidth, but if you've got a big library, it'll take a long time anyway.
One last thing: you can run either of these applications on your Synology, but if it's easier for you, just mount your Synology drive on another computer and run the software there. Know that different cameras and phones can store the captured-at time in a ton of different tags: (btw: ExifTool won't parse datestamps from sibling files or from pathnames: that's exclusive afaik to PhotoStructure). If you'd rather use a UI, you can use PhotoStructure's " automatic organization" feature (which uses ExifTool under the hood). Is an example, and if you search on his forum there are many other worked examples.
If you're comfortable with the command line, this is easy to do with ExifTool.
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