Flowers that still look fresh and unfinished mean too early; once they have matured and most pistils have darkened and curled in, the plant is at its peak; wait much longer and it is moving on. Most growers harvest when the plant shows the ripeness signs the breeder or seed supplier gives. Exact percentages are a community rule of thumb and personal taste, not a measured standard. Check flowers from several spots in the plant, not just the top.
Breeders usually list flowering time, which gives a window to start looking. When it is time, have the trimming tools ready.

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