Deducing the conformational space for an octa-proline helix.

A molecular dyad, PY-P8-PER, comprising a proline octamer sandwiched between pyrene and perylene terminals has been synthesized in order to address the dynamics of electronic energy transfer (EET) along the oligo-proline chain. A simple pyrene-based control compound equipped with a bis-proline attachment serves as a reference for spectroscopic studies. The N-H NMR signal at the terminal pyrene allows distinction between cis and trans amides and, although the crystal structure for the control has the trans conformation, temperature-dependent NMR studies provide clear evidence for trans/cis isomerisation in D6-DMSO. Polar solvents tend to stabilise the trans structure for the pyrene amide group, even for longer oligo-proline units. Circular dichroism shows that the proline spacer for PY-P8-PER exists mainly in the all-trans geometry in methanol. Preferential excitation of the pyrene chromophore is possible at wavelengths in the 320-350 nm range and, for the dyad, is followed by efficacious EET to the perylene emitter. The probability for intramolecular EET, obtained from analysis of steady-state spectroscopic data, is ca. 80-90% in solvents of disparate polarity. Comparison with the Förster critical distance suggests the terminals are ca. 18 Å apart. Time-resolved fluorescence spectroscopy, in conjunction with DFT calculations, indicates the dyad exists as a handful of conformers displaying a narrow range of EET rates. Optimisation of a distributive model allows accurate simulation of the EET dynamics in terms of reasonable structures based on isomerisation of certain amide groups.

Stereochemical Control of Secondary Benzamide-based BODIPY Emitters.

Aromatic amides can be used to construct light-harvesting materials with valuable optical properties. The amide bond is formed using well-known coupling agents in near quantitative yield, as illustrated here through the synthesis of two boron dipyrromethene derivatives bearing an amide linkage. The primary concern with acyl amides is rotation around the C-N bond, leading to cis and trans isomers. Using NMR spectroscopy, quantum chemical calculations and critical comparison to simpler benzamides, the stereochemistry of the target compounds has been addressed. The N-cyclohexyl derivative gave diffraction quality crystals that established a trans geometry for the amide bond. Quantum chemical calculations support the trans geometry as being the lowest-energy structure in solution but indicate that inversion of the aryl ring is an important structural feature. Indeed, rotation around the C(sp2 )-C(aryl) bond has a strong influence on the solution-phase NMR spectra. The amide connection has minimal effect on the photophysical properties.

Light-Harvesting Crystals Formed from BODIPY-Proline Biohybrid Conjugates: Antenna Effects and Excitonic Coupling.

A boron dipyrromethene (BODIPY) derivative bearing a cis-proline residue at the meso-position crystallizes in the form of platelets with strong (i.e., ΦF = 0.34) red fluorescence, but the absorption and emission spectra differ markedly from those for dilute solutions. A key building block for the crystal is a pseudo-dimer where hydrogen bonding aligns the proline groups and separates the terminal chromophores by ca. 25 Å. Comparison with a covalently linked bichromophore suggests that one-dimensional (1D) excitonic coupling between the terminals is too small to perturb the optical properties. However, accretion of the pseudo-dimer forms narrow channels possessing a high density of chromophores. The resultant absorption spectrum exhibits strong excitonic splitting, which can be explained quantitatively using the extended dipole approach and allowing for coupling between ca. 30 BODIPY units. Fluorescence, which decays with a lifetime of 2.2 ns, is assigned to a delocalized and (slightly) super-radiant BODIPY dimer situated at the interface and populated via electronic energy transfer from the interior.