Absolutely not. You get three "innovation tokens"[1] to spend on any startup and if you spend one of them on getting a team to learn Phoenix you're short-handed right out of the gate. Choosing boring technology allows you to focus on the business/problem domain you're trying to solve and allows you to find more qualified engineers to help you get there.
If we've learned anything from Facebook it's that you can start out with a pure LAMP stack and scale to billions of users with selective re-engineering later if there's a need to scale (Twitter proves something similar with Ruby on Rails; I'm sure there are "boring" Python examples as well).