Azadipyrromethene cyclometalation in neutral Ru(II) complexes: photosensitizers with extended near-infrared absorption for solar energy conversion applications.

In the on-going quest to harvest near-infrared (NIR) photons for energy conversion applications, a novel family of neutral ruthenium(ii) sensitizers has been developed by cyclometalation of an azadipyrromethene chromophore. These rare examples of neutral ruthenium complexes based on polypyridine ligands exhibit an impressive panchromaticity achieved by the cyclometalation strategy, with strong light absorption in the 600-800 nm range that tails beyond 1100 nm in the terpyridine-based adducts. Evaluation of the potential for Dye-Sensitized Solar Cells (DSSC) and Organic Photovoltaic (OPV) applications is made through rationalization of the structure-property relationship by spectroscopic, electrochemical, X-ray structural and computational modelization investigations.

Stereoselective synthesis of the Halaven C14-C26 fragment from D-quinic acid: crystallization-induced diastereoselective transformation of an α-methyl nitrile.

Crystallization-induced diastereoselective transformation (CIDT) of an α-methyl nitrile completes an entirely non-chromatographic synthesis of the halichondrin B C14-C26 stereochemical array. The requisite α-methyl nitrile substrate is derived from D-quinic acid through a series of substrate-controlled stereoselective reactions via a number of crystalline intermediates that benefit from a rigid polycyclic template. Therefore, all four stereogenic centers in the Halaven C14-C26 fragment were derived from the single chiral source D-quinic acid.

Introducing asymmetry in tetradentate azadipyrromethene chromophores: a systematic study of the impact on electronic and photophysical properties.

As analogues of the porphyrinoid and dipyrromethene families of dye, azadipyrromethene (ADPM) derivatives exhibit exciting photophysical properties. Their high absorbance (ε up to 100,000 M(-1) cm(-1)) in the yellow-to-red region and the strong NIR luminescence encountered in boron-chelated aza-BODIPY analogues are especially interesting in the context of light-harvesting and life science applications. In the present study, we endeavoured to compare symmetric and asymmetric tetradentate ADPM derivatives 1-6 versus two related bidentate ADPM references in order to gain insights into their structure-property relationship.

Azadipyrromethene dye derivatives in coordination chemistry: the structure-property relationship in homoleptic metal(II) complexes.

As a chromophore closely related to dipyrromethene (DPM), the azadipyrromethene (ADPM) family has attracted much interest in the life sciences and optoelectronic fields. A high-yielding microwave-assisted synthesis is reported for new homoleptic complexes of cobalt(II), nickel(II), copper(II) and zinc(II) based on the tetrakis(p-methoxyphenyl)azadipyrromethene ligand 1b. These complexes are compared with other homoleptic complexes of the same metal(II) series based on the tetraphenylazadipyrromethene 1a and also with related BF2(+) chelates (Aza-BODIPYs 6a and 6b) for a better understanding of trends arising from substitution of the chelate and/or the electron-donating effect of the p-methoxy substituents.

Inter- and intramolecular [4 + 1]-cycloadditions between electron-poor dienes and electron-rich carbenes.

Inter- and intramolecular [4 + 1]-annulations between dialkoxy carbenes and electron-deficient dienes afford mono- or bicyclic products in moderate to good yield.