American Chemical Society, Journal of Physical Chemistry B (Soft Condensed Matter and Biophysical Chemistry), 42(118), p. 12243-12250, 2014
DOI: 10.1021/jp508060z
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N-alkylated indanylidene-pyrroline based molecular switches mimic different aspects of the light-induced retinal chromophore isomerization in rhodopsin: the vertebrate dim-light visual pigment. In particular, they display similar ultrashort excited state lifetime, sub-picosecond photoproduct appearance time and photoproduct vibrational coherence. To better understand the early light-induced dynamics of such systems, we have measured and modelled the resonance Raman spectra of the Z-isomer of the N-methyl-4-(5'-methoxy-2',2'-dimethyl-indan-1'-ylidene)-5-methyl-2,3-dihydro-2H-pyrrolium (NAIP) switch in methanol solution. It is shown that the data, complemented with a <70 fs excited-state trajectory computation, demonstrate an initial excited-state structural dynamics dominated by double-bond expansion and single-bond contraction stretches which subsequently coupled with a five-membered ring inversion and double-bond torsion. These results are discussed in the context of the mechanism of the excited-state photoisomerization of NAIP switches in solution and the 11-cis retinal in rhodopsin.