^^ No. You have to be on instruments.
FAR 61.51
(g) Logging instrument flight time. (1) A person may log instrument time only for that flight time when the person operates the aircraft solely by reference to instruments under actual or simulated instrument flight conditions.
If you are at FL 350, 100' above a solid overcast, you are in VMC on an IFR flight plan. You can't log instrument time because you can fly without looking at your instruments.