Is the LEGOSTORE100-1 set rare given its small piece count?

Yes, as a special event set from the 2013 Grand Opening, this 5-piece set is a specific collectible item.

What is the theme of this particular LEGO set?

The theme for this set is the LEGO Brand Store.

It commemorates the 100th LEGO Store Grand Opening event in White Plains, NY, in 2013.

Name: LEGO LEGO Store 100th LEGO Store Grand Opening Set, White Plains, NY, June 28-30, 2013 (LEGOSTORE100-1)
Brand: LEGO

LEGO Brand Store

LEGO Brand Store · 2013

Theme · LEGO Brand StorePieces · 5Set Number · LEGOSTORE100-1Year · 2013

Used

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New / Sealed

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Is the LEGOSTORE100-1 set rare given its small piece count?: Yes, as a special event set from the 2013 Grand Opening, this 5-piece set is a specific collectible item.
What is the theme of this particular LEGO set?: The theme for this set is the LEGO Brand Store.
When and where was this set associated with?: It commemorates the 100th LEGO Store Grand Opening event in White Plains, NY, in 2013.