If you're one of those folks looking for that golden, sunkissed look to your portraiture then what you genuinely want is the entire period of the golden hour--and ideally before it. In big cities like in New York, sundown can last for a number of hours.
The sun gets really nice and warm--so when combined with 5600K white balance (or auto, I guess) you can make skin tones really pop. But if you're the type of person that can't always wait for the sun to give you what nature does best, then seriously consider that the best time to take outdoor portraits is truthfully any time of the day. . thephoblographer.com