Photoregulated Transmembrane Charge Separation by Linked Spiropyran−Anthraquinone Molecules

• Published in: Journal of the American Chemical Society 2006-01, Vol.128 (3), p.825-835
• Main Authors: Zhu, Linyong, Khairutdinov, Rafail F, Cape, Jonathan L, Hurst, James K
• Format: Article
• Language: English
• Subjects: 2,2'-Dipyridyl - analogs & derivatives; 2,2'-Dipyridyl - chemistry; Anthraquinones - chemistry; Atomic and molecular physics; Benzopyrans - chemistry; Edetic Acid - chemistry; Exact sciences and technology; Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion); Indoles - chemistry; Kinetics; Membranes, Artificial; Metalloporphyrins - chemistry; Molecular properties and interactions with photons; Nitro Compounds - chemistry; Organometallic Compounds - chemistry; Oxidation-Reduction; Phosphatidylcholines - chemistry; Photochemistry; Physics; Quantum Theory; Radiationless transitions, quenching; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0545620

Amide-linked spiropyran−anthraquinone (SP−AQ) conjugates were shown to mediate ZnTPPS4--photosensitized transmembrane reduction of occluded Co(bpy)3 3+ within unilamellar phosphatidylcholine vesicles by external EDTA. Overall quantum yields for these reactions were dependent upon the isomeric state of the dye; specifically, 30−35% photoconversion of the closed-ring spiropyran (SP) moiety to the open-ring merocyanine (MC) form caused the quantum yield to decrease by 6-fold in the simple conjugate and 3-fold for an analogue containing a lipophilic 4-dodecylphenoxy substituent on the anthraquinone moiety. Transient spectroscopic and fluorescence quenching measurements revealed that two factors contributed to these photoisomerization-induced changes in quantum yields:  increased efficiencies of fluorescence quenching of 1ZnTPPS4- by the merocyanine group and lowered transmembrane diffusion rates of the merocyanine-containing redox carriers. Transient spectrophotometry also revealed the sequential formation and decay of two reaction intermediates, identified as 3ZnTPPS4- and a species with the optical properties of a semiquinone radical. Kinetic profiles for Co(bpy)3 3+ reduction under continuous photolysis in the presence and absence of added ionophores indicated that transmembrane redox mediated by SP-AQ was electroneutral, but reaction by the other quinone-containing mediators was electrogenic. The minimal reaction mechanism suggested from the combined studies is oxidative quenching of vesicle-bound 3ZnTPPS4- by the anthraquinone unit, followed by either H+/e- cotransport by transmembrane diffusion of SP-AQH• or, for the other redox mediators, semiquinone anion-quinone electron exchange leading to net transmembrane electron transfer, with subsequent one-electron reduction of the internal Co(bpy)3 3+. Thermal one-electron reduction of Co(bpy)3 3+ by EDTA is energetically unfavorable; the photosensitized reaction therefore occurs with partial conversion of photonic energy to chemical and transmembrane electrochemical potentials.