Search

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 "pigments". These are self-assembled bacteriochlorophyll c, d, and e derivatives, which consist of a chlorophyll skeleton bearing a 3(1)-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 π-stacking, hydrogen bonding, and metal-oxygen 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 3(1)-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 17(2)-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.

Conductive tubes: Self-assembled nanotubes of a bacteriochlorophyll derivative are reminiscent of natural chlorosomal light-harvesting assemblies. After deposition on a substrate that consists of a non-conductive silicon oxide surface (see picture, brown) and contacting the chlorin nanowires to a conductive polymer (yellow), they show exceptional charge-transport properties., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new chlorophyll derivative with peripheral olefinic chains has been synthesised and its self-assembly properties have been studied, revealing formation of well-defined nanorods. These nanorods were stabilized and rigidified by olefin metathesis reaction as confirmed by spectroscopic and microscopic methods.

A chlorophyll derivative with a central zinc ion, a methoxy functionality at its 3(1)-position, and functionalized with a second-generation dendron (3,4-3,4,5)12G2-CH(2)OH at its 17(2)-position was synthesized starting from natural chlorophyll a (Chl a). This compound exhibits liquid crystalline (LC) behavior and its mesomorphic properties have been characterized by differential scanning calorimetry (DSC), polarisation optical microscopy (POM), powder X-ray diffraction (XRD), and scanning probe microscopy (SPM). A combination of powder XRD, high resolution scanning tunneling microscopy (STM), and atomic force microscopy (AFM) experiments revealed the formation of nano-segregated well-ordered columnar tubular superstructures consisting of about five molecules in the column stratum. These self-assembled columns are further self-organized into a two-dimensional oblique unit cell lattice. Semiconducting behavior of this compound has been studied by pulse-radiolysis time-resolved microwave conductivity (PR-TRMC) method and charge carrier mobility values of ∼10(-2) cm(2) V(-1) s(-1) are observed. Such organized columnar superstructures constructed from semisynthetic zinc chlorins are reminiscent of the tubular organization of the bacteriochlorophyll dyes in the light-harvesting chlorosomal antennae of green sulphur bacteria., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The highly efficient, light-harvesting antennae systems present in chlorosomes of green phototrophic bacteria, such as Chloroflexus aurantiacus, serve as a model for the design of bioinspired nanostructured materials. A semisynthetic zinc chlorin, derived from natural chlorophyll a, is used as a building block that self-assembles into excitonically coupled chromophore stacks. Temperature-dependent UV/Vis and circular dichroism spectroscopic measurements show the reversible formation of soluble chiral aggregates of this new zinc chlorin dye. High-resolution scanning tunneling microscopy and atomic force microscopy studies reveal the formation of two types of well-ordered pi-stacked aggregates on highly ordered pyrolytic graphite.

A series of three perylene tetracarboxylic acid bisimide dyes 3a-c bearing phenoxy substituents at the four bay positions of the perylene core were synthesized and their complexation behavior to complementary ditopic dialkyl melamines 8a-c was investigated. Binding constants and Gibbs binding energies for the hydrogen bonds between the imide and the complementary melamine moiety have been determined in several solvents by NMR and UV/Vis titration experiments with monotopic model compounds 5 and 9. The effects of the solvent polarity and specific solvent-solute interactions on the degree of polymerization of (3 x 8)n are discussed, and a general formula to estimate the chain length of [AA-BB]n nylon-type supramolecular polymers is derived. In addition to the formation of a hydrogen-bonded supramolecular chain. pi-pi interactions were observed for perylene bisimide-melamine assemblies 3b x 8b and 3b x 8c in aliphatic solvents. The orthogonal nature of hydrogen bonding and pi-pi interactions leads to three-dimensional growth yielding large-sized aggregates already in dilute solution. On suitable substrates, densely intertwined networks of nano- to mesoscopic strands are formed which have been investigated by electron microscopy, confocal fluorescence microscopy and optical polarization microscopy. The high fluorescence and excellent photostability of these superstructures is promising for future studies on energy migration and artificial light harvesting at the nano- and mesoscopic length scale.