Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates.

Elucidating the factors that control charge transfer rates in relatively flexible conjugates is of importance for understanding energy flows in biology as well as assisting the design and construction of electronic devices. Here, we report ultrafast electron transfer (ET) and hole transfer (HT) between a corrole (Cor) donor linked to a perylene-diimide (PDI) acceptor by a tetrameric alanine (Ala)4 Selective photoexcitation of the donor and acceptor triggers subpicosecond and picosecond ET and HT. Replacement of the (Ala)4 linker with either a single alanine or phenylalanine does not substantially affect the ET and HT kinetics. We infer that electronic coupling in these reactions is not mediated by tetrapeptide backbone nor by direct donor-acceptor interactions. Employing a combination of NMR, circular dichroism, and computational studies, we show that intramolecular hydrogen bonding brings the donor and the acceptor into proximity in a "scorpion-shaped" molecular architecture, thereby accounting for the unusually high ET and HT rates. Photoinduced charge transfer relies on a (Cor)NH…O=C-NH…O=C(PDI) electronic-coupling pathway involving two pivotal hydrogen bonds and a central amide group as a mediator. Our work provides guidelines for construction of effective donor-acceptor assemblies linked by long flexible bridges as well as insights into structural motifs for mediating ET and HT in proteins.

How does tautomerization affect the excited-state dynamics of an amino acid-derivatized corrole?

In the first two decades of the XXI century, corroles have emerged as an important class of porphyrinoids for photonics and biomedical photonics. In comparison with porphyrins, corroles have lower molecular symmetry and higher electron density, which leads to uniquely complementary properties. In macrocycles of free-base corroles, for example, three protons are distributed among four pyrrole nitrogens. It results in distinct tautomers that have different thermodynamic energies. Herein, we focus on the excited-state dynamics of a corrole modified with L-phenylalanine. The tautomerization in the singlet-excited state occurs in the timescales of about 10-100 picoseconds and exhibits substantial kinetic isotope effects. It, however, does not discernably affect nanosecond deactivation of the photoexcited corrole and its basic photophysics. Nevertheless, this excited-state tautomerization dynamics can strongly affect photoinduced processes with comparable or shorter timescales, considering the 100-meV energy differences between the tautomers in the excited state. The effects on the kinetics of charge transfer and energy transfer, initiated prior to reaching the equilibrium thermalization of the excited-state tautomer population, can be indeed substantial. Such considerations are crucially important in the design of systems for artificial photosynthesis and other forms of energy conversion and charge transduction.

Covalently Linked Bis(Amido-Corroles): Inter- and Intramolecular Hydrogen-Bond-Driven Supramolecular Assembly.

Four bis-corroles linked by diamide bridges were synthesized through peptide-type coupling of a trans-A2 B-corrole acid with aliphatic and aromatic diamines. In the solid state, the hydrogen-bond pattern in these bis-corroles is strongly affected by the type of solvent used in the crystallization process. Although intramolecular hydrogen bonds play a decisive role, they are supported by intermolecular hydrogen bonds and weak N-H⋅⋅⋅π interactions between molecules of toluene and the corrole cores. In an analogy to mono(amido-corroles), both in crystalline state and in solutions, the aliphatic or aromatic bridge is located directly above the corrole ring. When either ethylenediamine or 2,3-diaminonaphthalene are used as linkers, incorporation of polar solvents into the crystalline lattice causes a roughly parallel orientation of the corrole rings. At the same time, both NHCO⋅⋅⋅NH corrole hydrogen bonds are intramolecular. In contrast, solvation in toluene causes a distortion with one of the hydrogen bonds being intermolecular. Interestingly, intramolecular hydrogen bonds are always formed between the -NHCO- functionality located further from the benzene ring present at the position 10-meso. In solution, the hydrogen-bonds pattern of the bis(amido-corroles) is strongly affected by the type of the solvent. Compared with toluene (strongly high-field shifted signals), DMSO and pyridine disrupt self-assembly, whereas hexafluoroisopropanol strengthens intramolecular hydrogen bonds.

Synthesis of Corroles and Their Heteroanalogs.

Corroles have come a long way from being a curiosity to being a mainstream research topic. They are now regularly synthesized in numerous research laboratories worldwide with diverse specific aims in mind. In this review we present a comprehensive description of corroles' synthesis, developed both before and after 1999. To aid the investigator in developing synthetic strategies, some of the sections culminate in tables containing comparisons of various methodologies leading to meso-substituted corroles. The remaining challenges are delineated. In the second part of this review, we also describe the syntheses of isocorroles and heteroanalogs of corroles such as triazacorroles (corrolazines), 10-heterocorroles, 21-heterocorroles, 22-heterocorroles, N-confused corroles, as well as norcorroles. The review is complemented with a short outlook.

Hydrogen Bonds Involving Cavity NH Protons Drives Supramolecular Oligomerization of Amido-Corroles.

trans-A2 B-Corroles with amide substituents at different positions versus the macrocyclic core have been synthesized. Their self-organizing properties have been comprehensively evaluated both in solid-state and in solution. The rigid arrangement of the amide functionality with the corrole ring led to the formation of strong intramolecular interactions and precluded intermolecular interactions. Replacement of sterically hindered C6 F5 substituents at positions 5 and 15 with smaller electron-withdrawing CO2 Me groups resulted in significant changes in the self-assembly pattern. With these substituents, tetramers formed in a crystalline state, in which one of the H-pyrrole subunits is out of the corrole plane. This allows the N-H group to form a hydrogen bond with a neighboring carbonyl group of the n-butyl amide fragment. DOSY NMR studies showed that amido-corroles bearing the OCH2 CONHnBu motif formed dimers in millimolar solutions in nonpolar solvents and the dimers existed in equilibrium with monomers. However, the corroles possessing meso-ester groups did not form dimers in polar tetrahydrofuran. Comprehensive optical studies allowed the absorption and emission features of the monomer corroles to be characterized in dilute solutions.

Strong solvent dependence of linear and non-linear optical properties of donor-acceptor type pyrrolo[3,2-b]pyrroles.

We describe the design, synthesis, and fluorescent profile of two environment-sensitive dyes in which an electron-donating group is conjugated to an electron-accepting unit via a pyrrolo[3,2-b]pyrrole ring system. The maximum emission wavelength (λem) of these donor-donor-acceptor (D-D-A) pyrrolo[3,2-b]pyrroles was found to be very sensitive to the environment (a bathochromic shift of about 100 nm in polar solvents). The longer emission wavelength in polar aprotic as well as hydrophilic solvents compared with that in low-polarity hydrophobic solvents was due to an ICT character of the excited state. The Stokes shift increased in both cases following the polarity differences, reaching ∼7000 cm(-1) in MeOH for the compound possessing a cyano group and dimethylamino groups at the periphery. Interestingly, the two-photon absorption responses were also found to be quite sensitive to solvent polarity with an increase by a factor of about 2 on going from an apolar solvent to a highly polar protic or aprotic solvent.

Self-assembling corroles.

trans-A2B-corroles bearing -OCH2CONHR groups at the ortho position of the meso-phenyl substituent undergo self-organization both in the solid state as well as in solution. The lack of additional donor atoms induces sheet formation, but if the pyridine unit is present in the structure, more complex helical forms are formed.