Search

In this work, we report the synthesis, spectroscopic characterization, and theoretical analysis of a linearly conjugated pentacene-fused porphyrin dimer and cross-conjugated quinone-fused dinaphtho[2,3]porphyrins. These multichromophoric systems display non-typical UVvisible absorptions of either porphyrins or pentacenes/quinones. UV-visible, emission and magnetic circular dichroism (MCD) spectroscopy suggest strong electronic interactions among the multichromophores in the system. DFT calculations revealed the delocalization of the HOMOs and LUMOs spanning the entire dimer and linker assembly. The pentacene-fused porphyrin dimer is significantly more stable than both the corresponding pentacene and the heptacene derivatives. The availability of these huge π-extended and electronically highly interactive multichromophoric systems promises unprecedented electronic and photophysical properties. [ABSTRACT FROM AUTHOR]

A series of dimeric ReI(CO)3 compounds have been prepared by means of a one-pot reaction of [Re(CO)5X] (X = Cl, Br), pyridine-2-carboxyaldehyde, and o-, m-, or p-phenylenediamine. For the m- and p-substituted phenylenediamine reactions, phenyl-bridged bis(pyridine-2-carbaldimine) compounds of the formula [Re(CO)3X]2(μ-PPC) [ 3- 7; X = Cl, Br; μ-PPC = m- or p-phenylene bis(pyridine-2-carbaldimine)] were produced, with m-phenylenediamine forming a mixture of isomers. For reactions with o-phenylenediamine, multiple products formed (compounds 8- 11), which ranged from the desired o-phenylene bis(pyridine-2-carbaldimine) adduct to 2-pyridylbenzimidazole and bridging dipyridinylquinoxaline complexes. An example of each complex was structurally elucidated by single-crystal X-ray methods. The dimeric m- and p-phenylene-bridged Re(CO)3X compounds, including a sulfonate derivative designed to improve solubility, were investigated for possible photophysical applications through the use of UV/Vis spectroscopy and cyclic voltammetry; the study revealed coupling between the rhenium centers. [ABSTRACT FROM AUTHOR]

The complexes [Ru(bpy)2(pyESO)](PF6)2 and [Os(bpy)2(pyESO)](PF6)2, in which bpy is 2,2′-bipyridine and pyESO is 2-((isopropylsulfinyl)ethyl)pyridine, were prepared and studied by 1H NMR, UV-visible and ultrafast transient absorption spectroscopy, as well as by electrochemical methods. Crystals suitable for X-ray structural analysis were grown for [Ru(bpy)2(pyESO)](PF6)2. Cyclic voltammograms of both complexes provide evidence for S→O and O→S isomerization as these voltammograms are described by an ECEC (electrochemical-chemical electrochemical-chemical) mechanism in which isomerization follows Ru2+ oxidation and Ru3+ reduction. The S- and O-bonded Ru3+/2+ couples appear at 1.30 and 0.76 V versus Ag/AgCl in propylene carbonate. For [Os(bpy)2(pyESO)](PF6)2, these couples appear at 0.97 and 0.32 V versus Ag/AgCl in acetonitrile, respectively. Charge-transfer excitation of [Ru(bpy)2(pyESO)](PF6)2 results in a significant change in the absorption spectrum. The S-bonded isomer of [Ru(bpy)2(pyESO)]2+ features a lowest energy absorption maximum at 390 nm and the O-bonded isomer absorbs at 480 nm. The quantum yield of isomerization in [Ru(bpy)2(pyESO)]2+ was found to be 0.58 in propylene carbonate and 0.86 in dichloroethane solution. Femtosecond transient absorption spectroscopic measurements were collected for both complexes, revealing time constants of isomerizations of 81 ps (propylene carbonate) and 47 ps (dichloroethane) in [Ru(bpy)2(pyESO)]2+. These data and a model for the isomerizing complex are presented. A striking conclusion from this analysis is that expansion of the chelate ring by a single methylene leads to an increase in the isomerization time constant by nearly two orders of magnitude. [ABSTRACT FROM AUTHOR]

The reaction of [Re(CO)3(H2O)3]Br or [Re(CO)5Cl] with two peptides, glycylglycine, or glycylalanine were investigated. Each reaction produced a unique, well-defined product. Structural elucidation showed the formation of chiral compounds with the formula [Re(CO)3(Gly-Xxx-O)]2, Xxx = Gly ( 1), Ala ( 2). Each dimer displays C2 symmetry and a nearly rectangular shape. The ligands are bound through the amine and amide carbonyl at a rhenium center and through the pendant carboxylate to the adjacent rhenium center. Both products are fully characterized by X-ray structure elucidation. [ABSTRACT FROM AUTHOR]