We monitor the time-dependent Stokes shift (TDSS) of fluorescence from the zwitterionic probe N-methyl-6-oxyquinolinium betaine in water. A spectral relaxation time tau(solv), = 0.57 ps (at 20.5 degrees C) is attributed to a solvation process involving water in the hydration layer. In this article we show that a tertiary butyl group, when attached to the chromophore, slows the dynamics to tau(solv), = 0.76 ps and increases the corresponding activation energy by 5 kJ/mol. In a companion paper (10.1021/acs.jpcb.7b05039), simulations suggest that the observed slow-down indicates coupling of solute vibrations to hydration water. Thus, a new angle on a thoroughly researched topic, solvation dynamics, has been opened.