Increased global demand for energy has led to prolific use of fossil fuels, which produce and release greenhouse gases, such as carbon dioxide. This increase in atmospheric carbon dioxide affects the global weather system and has been cited as a cause for global warming. For humans to continue to meet demands for energy while reducing greenhouse emission, a sustainable, carbon-neutral energy source must be developed. The sun provides energy for the majority of life on earth, as well as the energy stored in the chemical bonds of fossil fuels. This dissertation investigates systems inspired by the biological mechanism of solar energy capture and storage. In natural photosynthesis, organisms use chlorophyll as a chromophore to absorb the sun's energy. Bio-inspired systems use close analogues like porphyrins and phthalocyanines. In this dissertation, a soluble, semiconducting porphyrin is reported. The polymer was synthesized via a Buchwald-Hartwig style coupling of porphyrin monomers which produced a polyaniline-like chain with porphyrins incorporated into the backbone. Spectroscopic and electrochemical studies were performed, which show evidence of excited state charge transfer and a first oxidation state of 0.58 V (vs SCE). These properties suggest that the polymer could be involved in excited state electron donation to fullerenes and other electron acceptors, which could be beneficial in organic photovoltaics, sensors, and other applications. Molecular dyads and triads capable of charge separation have been studied for decades, and the spectroscopic properties of two novel systems are reported in this dissertation. A peripherally-connected zinc-phthalocyanine-C60 dyad was studied, and showed excited state electron transfer from the phthalocyanine excited state to the C60, with a long-lived charge separated state. An axially-linked carotene-Si-pthalocyanine-C60 triad was studied, showing excited state electron transfer from the phthalocyanine to the C60, but fast recombination before hole transfer can occur to the carotene. Analogues of the electron transport mechanisms used in many biological systems use iron-sulfur clusters to shuttle electrons from donors to acceptors. In this dissertation, the spectroscopic properties of a de novo protein were studied. Nanosecond transient absorption was used to characterize the electron and energy transfer of an excited water-soluble porphyrin to the oxidized [FeS] clusters incorporated in the de novo protein. The triplet state of the porphyrin was strongly quenched with the holo-protein without a rise in porphyrin plus signal, suggesting that only Dexter-type energy transfer occurs between the sensitized porphyrin and the [FeS] clusters.

Photochromic molecules, which photoisomerize between two chemically and optically distinct states, are well suited for electron and energy transfer to covalently attached chromophores. This dissertation aims to manipulate electron and energy transfer by photochromic control in a number of organic molecular systems. Herein the synthesis, characterization and function of these organic molecular systems will be described. Electron and energy transfer were quantified by the use of steady state absorbance and fluorescence, as well as time-resolved fluorescence and transient absorbance. A dithienylethene-porphrin-fullerene triad was synthesized to investigate photochromic control of photo-induced electron transfer. Control of two distinct electron transfer pathways was achieved by photochromic switching. A molecular dyad was synthesized, in which fluorescence was modulated by energy transfer by photoinduced isomerization. Also described is a triplet-triplet annihilation upconversion system that covalently attaches fluorophores to improve quantum yield. Overall these studies demonstrate complex molecular switching systems, which may lead to advancement in organic electronic applications and organic based artificial photosynthesis systems.

Nanoporous electrically conducting materials can be prepared with high specific pore volumes and surface areas which make them well-suited for a wide variety of technologies including separation, catalysis and owing to their conductivity, energy related applications like solar cells, batteries and capacitors. General synthetic methods for nanoporous conducting materials that exhibit fine property control as well as facility and efficiency in their implementation continue to be highly sought after. Here, general methods for the synthesis of nanoporous conducting materials and their characterization are presented. Antimony-doped tin oxide (ATO), a transparent conducting oxide (TCO), and nanoporous conducting carbon can be prepared through the step-wise synthesis of interpenetrating inorganic/organic networks using well-established sol-gel methodology. The one-pot method produces an inorganic gel first that encompasses a solution of organic precursors. The surface of the inorganic gel subsequently catalyzes the formation of an organic gel network that interpenetrates throughout the inorganic gel network. These mutually supporting gel networks strengthen one another and allow for the use of evaporative drying methods and heat treatments that would usually destroy the porosity of an unsupported gel network. The composite gel is then selectively treated to either remove the organic network to provide a porous inorganic network, as is the case for antimony-doped tin oxide, or the inorganic network can be removed to generate a porous carbon material. The method exhibits flexibility in that the pore structure of the final porous material can be modified through the variation of the synthetic conditions. Additionally, porous carbons of hierarchical pore size distributions can be prepared by using wet alumina gel as a template dispersion medium and as a template itself. Alumina gels exhibit thixotropy, which is the ability of a solid to be sheared to a liquid state and upon removal of the shear force, return to a solid gel state. Alumina gels were prepared and blended with monomer solutions and sacrificial template particles to produce wet gel composites. These composites could then be treated to remove the alumina and template particles to generate hierarchically porous carbon.