If I give away some of my inventory as promotional free gifts, is there a way of accounting for this as an advertising/promotional expense? (Rather than simply creating a sales invoice with a “100% discount” to keep the inventory numbers in order.)
Definitely you can by inventory write-offs
Enable inventory write-offs tab and continue it … as you read the Guides will explain to you everything
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https://www.manager.io/guides/10709
Always search the guides first, then the forum and if not sure, ask a question
So I should use a Delivery Note rather than an Invoice as a packing slip in this case?
No. A delivery note removes the item from inventory, which the write-off already did. If you want some sort of packing list, you should create one outside of Manager.
Please read the guides as recommended and linked to. It even provides an example of what yiou try to do and it is as @Tut and others say related to write-offs. You can assign these then to any expense account you have in P&L.
Mea culpa if I overlooked the guide about Inventory Write-offs. But from what Tut is saying, there is no way of creating a packing slip or mailing label in Manager when you’re shipping a customer a free sample, which was my next question.
there is no way of creating a packing slip or mailing label in Manager
That is not true. You can create a zero value sales invoice and delivery note as mentioned above. But it is more work. And Manager has no mailing labels anyway.
I am using the term “mailing label” in a broad/loose sense… I usually insert a folded Manager invoice inside a “labelope” when shipping items.
By “zero value invoice”, do you mean I should write “Free Widget - 1” in the Description and Qty fields, and leave the Item and Account fields blank?
No. You should select the item, enter the quantity, but enter a zero unit price. Then enter the delivery note.
No. You should select the item, enter the quantity, but enter a zero unit price. Then enter the delivery note.
But I’ve already entered 1x free widget as an inventory write-off (as suggested above), claiming it as a Promotional/Advertising expense. Surely creating a separate sales invoice and/or delivery note and entering 1x widget with a zero unit price will mess up my inventory totals?
You need to do one approach or the other. After being told the accepted method was an inventory writeoff, you said you wanted to generate a mailing label (effectively a packing list) within Manager. So I told you how. I did not say you should do both.
I would prefer not to create a packing slip outside of Manager if I can avoid it. 
As a “workaround” I created an invoice for the customer’s free sample and then deleted the invoice.