Chlorophyll J-Aggregates: From Bioinspired Dye Stacks to Nanotubes, Liquid Crystals, and Biosupramolecular Electronics
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- 作者：Sanchita Sengupta ; Frank W眉rthner
- 刊名：Accounts of Chemical Research
- 出版年：2013
- 出版时间：November 19, 2013
- 年：2013
- 卷：46
- 期：11
- 页码：2498-2512
- 全文大小：1368K
- 年卷期：v.46,no.11(November 19, 2013)
- ISSN：1520-4898
文摘
Among the natural light-harvesting (LH) systems, those of green sulfur and nonsulfur photosynthetic bacteria are exceptional because they lack the support of a protein matrix. Instead, these so-called chlorosomes are based solely on 鈥減igments鈥? These are self-assembled bacteriochlorophyll c, d, and e derivatives, which consist of a chlorophyll skeleton bearing a 31-hydroxy functional group. Chemists consider the latter as an essential structural unit to direct the formation of light-harvesting self-assembled dye aggregates with J-type excitonic coupling. The intriguing properties of chlorosomal J-type aggregates, particularly narrow red-shifted absorption bands, compared with monomers and their ability to delocalize and migrate excitons, have inspired intense research activities toward synthetic analogues in this field. The ultimate goal of this research field is the development of (opto-)electronic devices based on the architectural principle of chlorosomal LH systems. In this regard, the challenge is to develop small, functional building blocks with appropriate substituents that are preprogrammed to self-assemble across different length scales and to emulate functions of natural LH systems or to realize entirely new functions beyond those found in nature. In this Account, we highlight our achievements in the past decade with semisynthetic zinc chlorins (ZnChls) as model compounds of bacteriochlorophylls obtained from the naturally most abundant chlorin precursor: chlorophyll a.
To begin, we explore how supramolecular strategies involving 蟺-stacking, hydrogen bonding, and metal鈥搊xygen coordination can be used to design ZnChl-based molecular stack, tube, and liquid crystalline assemblies conducive to charge and energy transport. Our design principle is based on the bioinspired functionalization of the 31-position of ZnChl with a hydroxy or methoxy group; the former gives rise to tubular assemblies, whereas the latter induces stack assemblies. Functionalization of the 172-position with esterified hydrophilic or hydrophobic chains, dendron-wedge substituents, and chromophores having complementary optical properties such as naphthalene bisimides (NBIs) is used to modulate the self-assembly of ZnChl dyes. The resulting assemblies exhibit enhanced charge transport and energy transfer abilities. We have used UV/vis, circular dichroism (CD), fluorescence spectroscopy, and dynamic light scattering (DLS) for the characterization of these assemblies in solution. In addition, we have studied assembly morphologies by atomic force microscopy (AFM), scanning tunneling microscopy (STM), transmission electron microscopy (TEM), and cryogenic-TEM. Crystallographic techniques such as powder X-ray and solid-state NMR have been used to explain the precise long- and short-range packing of dyes in these assemblies. Finally, functional properties such as charge and energy transport have been explored by pulse radiolysis time-resolved microwave conductivity (PR-TRMC), conductive AFM, and time-resolved fluorescence spectroscopy. The design principles discussed in this Account are important steps toward the utilization of these materials in biosupramolecular electronics and photonics in the future.
To begin, we explore how supramolecular strategies involving 蟺-stacking, hydrogen bonding, and metal鈥搊xygen coordination can be used to design ZnChl-based molecular stack, tube, and liquid crystalline assemblies conducive to charge and energy transport. Our design principle is based on the bioinspired functionalization of the 31-position of ZnChl with a hydroxy or methoxy group; the former gives rise to tubular assemblies, whereas the latter induces stack assemblies. Functionalization of the 172-position with esterified hydrophilic or hydrophobic chains, dendron-wedge substituents, and chromophores having complementary optical properties such as naphthalene bisimides (NBIs) is used to modulate the self-assembly of ZnChl dyes. The resulting assemblies exhibit enhanced charge transport and energy transfer abilities. We have used UV/vis, circular dichroism (CD), fluorescence spectroscopy, and dynamic light scattering (DLS) for the characterization of these assemblies in solution. In addition, we have studied assembly morphologies by atomic force microscopy (AFM), scanning tunneling microscopy (STM), transmission electron microscopy (TEM), and cryogenic-TEM. Crystallographic techniques such as powder X-ray and solid-state NMR have been used to explain the precise long- and short-range packing of dyes in these assemblies. Finally, functional properties such as charge and energy transport have been explored by pulse radiolysis time-resolved microwave conductivity (PR-TRMC), conductive AFM, and time-resolved fluorescence spectroscopy. The design principles discussed in this Account are important steps toward the utilization of these materials in biosupramolecular electronics and photonics in the future.