I have a few timer ones, which cost buttons, and it's fairly effective. Hearing the radiators turn off reminds me to go to bed.
I also have a Nest, which is good if your whole house it evenly temperate. Mine isn't, so my Nest sits in a room with the radiators off at night, and it gets cranked up and down to keep the kids bedroom within a temperature range using a "Sensepeanut". That's a Bluetooth temperature sensor and phone app, which can control the app directly or via IFTTT I have it do both because, on a few occasions one or other hasn't worked.
I'd be interested in a good valve setup. Honeywell seems to give a lot of what you want, but without any of the finesse of these apps. The valves I have say a temperature number... But they really just mean "how much of the valve is open" because they have never once adjusted themselves.
Despite all of these things, I haven't seen any massive savings, but the bedrooms get toasty quickly at night.