Hi! You're right, you can use the Line of Sight behavior.
Just like in real life, you know that a point is in shadow if there is an obstacle between the line that connects the point itself to the light source. We can use this to check if a specific point is on shadow or not. Simply check the LOS between the point coordinates and the sun coordinates.
If you have a big sprite with complex geometry and you want to check if that sprite is on shadow, you need to repeat the same thing, but with all collision polygon points. If no collision point has line of sight with the sun, then the whole object is in shadow.
Since Construct doesn't provide a simple way to get the collision polygon points in the event sheet, you can use image points placed at the position of the collision polygon points, and test if those points have line of sight with the sun.
I made a small working prototype that implement this mechanic: dropbox.com/scl/fi/5ocbuher2dshq0yyz3wqr/Shadow-collision.c3p