What Compendium entries cannot be bought from Purah's Assistant?

Once Purah unlocks the Camera function at the Hateno Tech Lab, her assistant offers to fill in your Hyrule Compendium in exchange for rupees - 100 for each entry. I spent a good amount of rupees buying every entry I could, and I've reached the point where he no longer has anything left to sell me, but I still have a handful of creatures and weapons I haven't discovered yet. What entries am I missing, and how do I get them?

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3 Answers

After defeating Ganon, and entering the post-game, the following extra pictures can be purchased at 500 Rupees per picture, in the "Elite Enemies" section:

• All Silver Enemies (e.g. Silver Lynel, Silver Moblin, Silver Bokoblin, etc.)
• All one-time only enemies (e.g. Bosses)

The following picture can also be purchased for 100 Rupees, in the "Weapons" category:

• Light Bow

After reading the comments on my question, I realized I had purchased all the pictures after facing the final Divine Beast and before fighting Ganon. Turns out I had two pictures that were available to purchase; a weapon and an "Elite Enemy" picture, a new category with a gold icon that was not there before I fought Ganon. The weapon was the Light Bow, and the Elite Enemy was Master Kohga. Upon purchasing these, Symin informed me that I had obtained every picture in the compendium. So it turns out there is an opportunity to purchase previously unbuyable pictures post-game.

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The strict answer to the question "what Compendium entries cannot be bought from Purah's Assistant?" is that there is precisely one (1) item that cannot be purchased and must be photographed by the player. The good news, is that it's not missable. This unique compendium entry is.....

The sunshroom.

In order to unlock the option to purchase pictures from Symin, you need to take a picture of a sunshroom and show it to him. Once you have logged a personal picture of an item, it's removed from the available pictures to purchase. According to a Gamefaqs thread, a "default" sunshroom picture does exist in the game files (pictured above), but it's impossible to obtain in-game. The linked thread does claim to have found the actual sunshroom in the default picture and offers a location and time of day to recreate the default picture.

Source: I completed a Hyrule compendium using only purchased picture and an ungodly number of rupees