In my humble opinion, if you confident the purity of methanol 100% (namely methanol extra pure grade), the experiment will be better result. However, if the methanol 100% was not available, the lower purity methanol should be dewatered using a double distillation system. According to the existance cirumstances, it is usually to use both methods for such an experiments.
Agree with Vladimir, above. It makes sense to use an extraction solution that can immediately solubilize hydrophobic ( high methanol) as well as hydrophilic molecules (30% water in the precipitation solution).
If you use 100% methanol, you may not be efficiently capturing the water soluble compounds.
here you didn't tell about which type of metabolites.
Generally it depends on the solubility of metabolites.
If it is totally soluble in methanol, then only we can use 100% methanol, otherwise 70% is best because, there is also a chance of methanol evaporation during the extraction if you use 100% methanol and you will not able to calculate exact amount of your interest metabolite.