A Solvation/Desolvation Indicator Based on van der Waals Interactions between Solvents and Porphyrins.

Solvation is a ubiquitous phenomenon associated with molecules in solutions. It often determines the equilibria of molecular systems and the rates of chemical reactions. Van der Waals interactions (a general term) includes weak interactions among noncharged compounds and it contributes significantly to solvation. The distinct observation of van der Waals interaction between solvent and porphyrin derivatives is reported herein. Bis(imidazolylporphyrinatozinc) structures connected through a 1,3-butadiyne moiety give two types of coordination polymers, E (extended) and S (stacked) polymers, exclusively. E polymers have larger solvent-accessible surface areas than the corresponding S polymers. Therefore, E polymers are better solvated than S polymers, providing an indicator of solvation and desolvation for the solvents used. A simple method (like a litmus test) was developed to evaluate the solvation ability of various solvents. Sixty-seven solvents and liquid compounds were tested, under the same conditions, using a conventional UV/Vis spectrometer. The results revealed a new liquid group with high solvation ability towards the porphyrins, and clarified van der Waals interaction assisted by secondary interaction on the substituents. The indicator system should contribute to the solution chemistry of molecules and materials, and to supramolecular chemistry interactions among hetero components.

Conjugation-length dependence of the T1 lifetimes of carotenoids free in solution and incorporated into the LH2, LH1, RC, and RC-LH1 complexes: possible mechanisms of triplet-energy dissipation.

In addition to the roles of antioxidant and spacer, carotenoids (Cars) in purple photosynthetic bacteria pursue two physiological functions, i.e., light harvesting and photoprotection. To reveal the mechanisms of the photoprotective function, i.e., quenching triplet bacteriochlorophyll to prevent the sensitized generation of singlet oxygen, the triplet absorption spectra were recorded for Cars, where the number of conjugated double bonds (n) is in the region of 9-13, to determine the dependence on n of the triplet lifetime. The Cars examined include those in (a) solution; (b) the reconstituted LH1 complexes; (c) the native LH2 complexes from Rba. sphaeroides G1C, Rba. sphaeroides 2.4.1, Rsp. molischianum, and Rps. acidophila 10050; (d) the RCs from Rba. sphaeroides G1C, Rba. sphaeroides 2.4.1, and Rsp. rubrum S1; and (e) the RC-LH1 complexes from Rba. sphaeroides G1C, Rba. sphaeroides 2.4.1, Rsp. molischianum, Rps. acidophila 10050, and Rsp. rubrum S1. The results lead us to propose the following mechanisms: (i) A substantial shift of the linear dependence to shorter lifetimes on going from solution to the LH2 complex was ascribed to the twisting of the Car conjugated chain. (ii) A substantial decrease in the slope of the linear dependence on going from the reconstituted LH1 to the LH1 component of the RC-LH1 complex was ascribed to the minor-component Car forming a leak channel of triplet energy. (iii) The loss of conjugation-length dependence on going from the isolated RC to the RC component of the RC-LH1 complex was ascribed to the presence of a triplet-energy reservoir consisting of bacteriochlorophylls in the RC component.