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cis (Z ) (b)

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Figure 1.3. (a) Azobenzene can convert between trans and cis states photochemically and relaxes to the more stable trans state thermally. (b) Simpli ed state model for azobenzenes. The trans and cis extinction coef cients are denoted by etrans and ecis. The F refer to quantum yields of photoisomerization, and g is the thermal relaxation rate constant.

These sphotoisomerizations usually have picosecond timescales (Lednev et al, 1996; Kobayashi et al, 1979) Alternately, azos will thermally reconvert from the cis into trans state, with a timescale ranging from milliseconds to hours, depending on the substitution pattern and local environment More speci cally, the lifetimes for azobenzenes, aminoazobenzenes, and pseudo-stilbenes are usually on the order of hours, minutes, and seconds, respectively The energy barrier for thermal isomerization is on the order of 90 kJ mol 1 (Brown and Granneman, 1975; Haber eld et al, 1975) Considerable work has gone into elongating the cis lifetime, with the goal of creating truly bistable photoswitchable systems Bulky ring substituents can be used to hinder the thermal back reaction For instance, a polyurethane main-chain azo exhibited a lifetime of 4 days (thermal rate constant of k=2.

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8 10 6 s 1, at 31C) (Lamarre and Sung, 1983), and an azobenzene parasubstituted with bulky pendants had a lifetime of 60 days (ko2 10 7 s 1, at room temperature) (Shirota et al, 1998) The conformational strain of macrocylic azo compounds can also be used to lock the cis state, where lifetimes of 20 days (k=59 10 7 s 1) (Norikane et al, 2003), 1 year (half-life 400 days, k=2 10 8 s 1) (Rottger and Rau, 1996; Rau and Roettger, 1994), or even 6 years (k=49 10 9 s 1) (Nagamani et al, 2005) were observed Similarly, using the hydrogen bonding of a peptide segment to generate a cyclic structure, a cis lifetime of B40 days (k=29 10 7 s 1) was demonstrated (Vollmer et al, 1999).

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