Two-Photon Absorption Properties and Structures of BODIPY and Its Dyad, Triad and Tetrad.

A series consisting of a dyad, a triad and a tetrad containing either two, three and four BODIPY units, respectively, has been synthesized and fully characterized and compared to two mono-BODIPY analogs (used as references). The one- and two-photon photophysical properties have been measured and the X-ray structures of four of the BODIPY derivatives have been determined. In the 700-900 nm range, the two-photon absorption (TPA) cross sections range from 30 GM to 160 GM for these compounds.

Alkyl- and aryl-substituted corroles. 4. Solvent effects on the electrochemical and spectral properties of cobalt corroles.

Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH(2)Cl(2), PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH(2)Cl(2), but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycl…

Non-linear optical, electrochemical and spectroelectrochemical properties of amphiphilic inner salt porphyrinic systems

Three zwitterionic meso-substituted A3B- and AB2C-porphyrins containing one sulfonato alkylpyridinium substituent and three or two alkoxy-substituted phenyl groups were synthesized in good yield and fully characterized as to their physicochemical properties by a variety of techniques. This new series of inner salt donor-acceptor meso-substituted porphyrin derivatives were prepared for possible application as amphiphilic probes for membrane insertion in the area of combined second-harmonic and two-photon fluorescence cellular microscopy. To this end, the linear and nonlinear optical properties of the compounds were characterized, together with their electrochemical and spectroelectrochemica…

Inside Cover: Synthesis and Characterization of Carbazole-Linked Porphyrin Tweezers (Chem. Eur. J. 34/2015)

Alkyl and aryl substituted corroles. 3. Reactions of cofacial cobalt biscorroles and porphyrin-corroles with pyridine and carbon monoxide.

The synthesis and characterization of three new cofacial biscorroles and three new linked Co(II) porphyrins and Co(III) corroles with the same face to face orientation are described. The biscorroles are represented as (BCS)Co(2), (BCO)Co(2), (BCX)Co(2) while the porphyrin-corrole dyads are represented as (PCA)Co(2), (PCB)Co(2), (PCO)Co(2) where BC represents the Co(III) cofacial biscorroles and PC represents the porphyrin-corrole complexes which are linked to each other by a dibenzothiophene (S), dibenzofuran (O), or 9,9-dimethylxanthene (X) bridge in the case of the corroles and an anthracene (A), biphenylene (B), or dibenzofuran (O) bridge in the case of the mixed macrocycle derivatives. …

Fine tuning of the photophysical properties of cofacial diporphyrins via the use of different spacers

The crystal and molecular structures of two unmetallated diporphyrin species using the biphenylene and dibenzofuran spacers, H4(DPB) and H4(DPO), respectively (DPB 4 − =1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene; DPO 4 − =4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzofuran), are reported. These data are compared to their literature metallated analogs, stressing on the properties related to the flexibility of the ligands, ··· and M···M interactions. In addition, the lowest energy fluorescence properties of these non-phosphorescent diporphyrin compounds as well as three other related species, H4(DPA), H4(DPX), and H4(DPS) (DPA 4 − …

Synthesis and Characterization of Carbazole-Linked Porphyrin Tweezers

Herein the synthesis, spectroscopic characterization, two-photon absorption and electrochemical properties of 3,6-disubstituted carbazole tweezers is reported. A dimer resulting from a Glaser homocoupling was isolated during a Sonogashira coupling reaction between a diethynyl-carbazole spacer and a 5-bromo-triarylporphyrin and the properties of this original compound were compared with the 3,6-disubstituted carbazole bisporphyrin tweezers. The dyads reported herein present a two-photon absorption maximum at 920 nm with two-photon absorption cross-section in the 1200 GM range. Despite a strong linear absorption in the Soret region and moderate fluorescence quantum yield, they both lead to a …

Luminescence properties of a cofacial dipalladium porphyrin dimer under argon and in the presence of dioxygen

The preparation and luminescence properties of a dipalladium cofacial porphyrin dimer (DPA) Pd 2 (where DPA is the tetraanion of 1,8-bis(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrin-5-yl)anthracene) are reported and compared together with the photophysical behavior of the known monomeric (OEP)Pd and (TPP)Pd complexes. The effect of dioxygen in the presence and in the absence of the very bulky base, 1-t-butyl-5-phenylimidazole, is also investigated. The title dimer, (DPA) Pd 2, shows fluorescence and phosphorescence in the ps and ms time scale, respectively, with a global intensity lower than that of the porphyrin monomer analogues. The fluorescence sensitivity towards dioxygen quenc…

Alkyl and Aryl Substituted Corroles. 1. Synthesis and Characterization of Free Base and Cobalt Containing Derivatives. X-ray Structure of (Me4Ph5Cor)Co(py)2

The synthesis, spectroscopic properties, and electrochemistry of six different alkyl- and aryl-substituted Co(III) corroles are presented. The investigated compounds contain methyl, ethyl, phenyl, or substituted phenyl groups at the eight β-positions of the corrole macrocycle and four derivatives also contain a phenyl group at the 10-meso position of the macrocycle. Each cobalt corrole undergoes four reversible oxidations in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate and exists as a dimer in its singly and doubly oxidized forms. The difference in potential between the first two oxidations is associated with the degree of interaction between the two corrole units of the dimer …

CCDC 1830060: Experimental Crystal Structure Determination

Related Article: Jian Yang, Yoann Rousselin, Léo Bucher, Nicolas Desbois, Frédéric Bolze, Hai-Jun Xu, Claude P. Gros|2018|ChemPlusChem|83|838|doi:10.1002/cplu.201800361

CCDC 1830057: Experimental Crystal Structure Determination

Related Article: Jian Yang, Yoann Rousselin, Léo Bucher, Nicolas Desbois, Frédéric Bolze, Hai-Jun Xu, Claude P. Gros|2018|ChemPlusChem|83|838|doi:10.1002/cplu.201800361

CCDC 1830059: Experimental Crystal Structure Determination

Related Article: Jian Yang, Yoann Rousselin, Léo Bucher, Nicolas Desbois, Frédéric Bolze, Hai-Jun Xu, Claude P. Gros|2018|ChemPlusChem|83|838|doi:10.1002/cplu.201800361

CCDC 1830058: Experimental Crystal Structure Determination

Related Article: Jian Yang, Yoann Rousselin, Léo Bucher, Nicolas Desbois, Frédéric Bolze, Hai-Jun Xu, Claude P. Gros|2018|ChemPlusChem|83|838|doi:10.1002/cplu.201800361