I like how twilight in this painting is used to illuminate infrastructure from behind. Twilight sets a somber and peaceful mood, as the sun will be setting soon. The light from behind is enough that we can see reflections in the water on the left and it adds a sense of clarity. However, we are unable to make out a clear shape on the right side, where light and distance are obscuring our vision of the rest of the skyline. Ability to see the reflections in the water parallels the sense of reflection that this time of day sets. The hues in this painting are visually pleasing and are blended well together throughout the painting.
From: https://commons.wikimedia.org/wiki/File:Claude_Monet_-_Twilight,_Venice.jpg
What you say about the twilight setting the mood has a very pleasing effect. I also think the way the twilight hues contrast with and silhouette the skyline also makes the figures more obscured and abstract. The calming effect of the reflection on the water is also present, with the colors paralleling each other in a very satisfying way.
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