A new class of porphyrin-based chromophore systems has been prepared from ethyne-elaborated porphyrin synthons through the use of metal-mediated cross-coupling methodologies. These systems feature porphyrin chromophores wired together through single ethynyl linkages. This type of topological connectivity affords exceptional electronic interactions between the chromophores which are manifest in their room temperature photophysics, optical spectroscopy, and electrochemistry; these spectroscopic signatures indicate that these species model many of the essential characteristics of biological light-harvesting antenna systems.

havior in PCET 3400 5.3. Adiabatic and Nonadiabatic PCET Interpreted in the Context of the Schrodinger Equation and the Born−Oppenheimer (Adiabatic) Approximation 3404 5.3.1. Quantum-State Dynamics of PCET Systems and the Underlying Potential (Free) Energy Surfaces 3404 5.3.2. Investigating Coupled Electronic−Nuclear Dynamics and Deviations from the Adiabatic Approximation in PCET Systems via a Simple Model 3408 5.3.3. Formulation and Representations of Electron−Proton States 6. Extension of Marcus Theory to Proton and Atom Transfer Reactions 6.1. Extended Marcus Theory for Electron, Proton, and Atom Transfer Reactions 6.2. Implications of the Extended Marcus Theory: Brønsted Slope, Kinetic Isotope Effect, and Cross-Relation 7. Beyond Marcus Theory: Nuclear Tunneling and Structural Constraints on PCET 8. Proton-Activated Electron Transfer: A Special Case of Separable and Coupled PT and ET 9. Dogonadze−Kuznetsov−Levich (DKL) Model of PT/HAT and Connections with ET and PCET Theories 10. Borgis−Hynes (BH) Theory for PT and HAT 10.1. Dynamical Regimes of the BH Theory 10.2. Splitting and Coupling Fluctuations 10.3. Reaction Rate Constant 10.4. Analytical Rate Constant Expressions in Limiting Regimes 11. Cukier Theory of PCET 11.1. Double-Adiabatic and Two-Dimensional Approaches 11.2. Reorganization and Solvation Free Energy in ET, PT, and EPT 11.3. Generalization of the Theory and Connections between PT, PCET, and HAT 12. Soudackov−Hammes-Schiffer (SHS) Theory of PCET 12.1. Regarding System Coordinates and Interactions: Hamiltonians and Free Energies 12.2. Electron−Proton States, Rate Constants, and Dynamical Effects 12.3. Note on the Kinetic Isotope Effect in PCET 12.4. Distinguishing between HAT and Concerted PCET Reactions 12.5. Electrochemical PCET 13. Conclusions and Prospects Appendix A Appendix B Associated Content Supporting Information

We demonstrate that synthetic soft materials can extend the utility of natural vesicles, from predominantly hydrophilic reservoirs to functional colloidal carriers that facilitate the biomedical application of large aqueous-insoluble compounds. Near-infrared (NIR)-emissive polymersomes (50-nm-to 50-m-diameter polymer vesicles) were generated through cooperative self assembly of amphiphilic diblock copolymers and conjugated multi(porphyrin)-based NIR fluorophores (NIRFs). When compared with natural vesicles comprised of phospholipids, polymersomes were uniquely capable of incorporating and uniformly distributing numerous large hydrophobic NIRFs exclusively in their lamellar membranes. Within these sequestered compartments, long polymer chains regulate the mean fluorophore-fluorophore interspatial separation as well as the fluorophore-localized electronic environment. Porphyrin-based NIRFs manifest photophysical properties within the polymersomal matrix akin to those established for these high-emission dipole strength fluorophores in organic solvents, thereby yielding uniquely emissive vesicles. Furthermore, the total fluorescence emanating from the assemblies gives rise to a localized optical signal of sufficient intensity to penetrate through the dense tumor tissue of a live animal. Robust NIR-emissive polymersomes thus define a soft matter platform with exceptional potential to facilitate deep-tissue fluorescence-based imaging for in vivo diagnostic and drug-delivery applications.porphyrin ͉ vesicles ͉ nanoscale ͉ diblock copolymer S upramolecular self assembly has revolutionized soft materials research by enabling the efficient and high-throughput fabrication of complex multicomponent nanostructures (1-3). For decades, self-assembled vesicles comprised of phospholipids (liposomes) or small-molecule surfactants (4) have been used for sequestering high concentrations of hydrophilic compounds (5) and controlling their temporal release and distribution for maximal therapeutic efficacy (6). More recently, amphiphilic peptides and polymers have been shown to form very elaborate architectures (7-9) and serve as useful nanocontainers in aqueous solution (10). In particular, self-assembled materials are ideal for carrying promising imaging and therapeutic agents whose biomedical utility has hitherto been hampered by inadequate aqueous solubility (11). Here, we demonstrate the unique ability of synthetic amphiphiles to assemble into functional vesicles that membrane-disperse numerous large hydrophobic fluorophores and enable their specialized application for deeptissue fluorescence-based in vivo imaging.Although visible probes enable exquisite imaging of live animals by intravital microscopy (12), their utility is significantly limited at greater than submillimeter tissue depths as a result of extensive light scattering and optical absorption. Because light scattering diminishes with increasing wavelength, and hemoglobin electronic and water vibrational overtone absorptions approach their nadir over the near-infrared (N...