A new general synthetic access to carboxylated quaterpyridines (qpy), of interest as ligands for panchromatic dye-sensitized solar cell organometallic sensitizers, is presented. The strategic step is a Suzuki-Miyaura cross-coupling reaction, which has allowed the preparation of a number of representative unsubstituted and alkyl and (hetero)aromatic substituted qpys. To bypass the poor inherent stability of 2-pyridylboronic acid derivatives, we successfully applied N-methyliminodiacetic acid (MIDA) boronates as key reagents, obtaining the qpy ligands in good yields up to (quasi)gram quantities. The structural, spectroscopic (NMR and UV-vis), electrochemical, and electronic characteristics of the qpy have been experimentally and computationally (DFT) investigated. The easy access to the bis-thiocyanato Ru(II) complex of the parent species of the qpy series, through an efficient route which bypasses the use of Sephadex column chromatography, is shown. The bis-thiocyanato Ru(II) complex has been spectroscopically (NMR and UV-vis), electrochemically, and computationally investigated, relating its properties to those of previously reported Ru(II)-qpy complexes.
Quaterpyridine ligands for panchromatic Ru(II) dye sensitizers
Lobello, Maria Grazia;De Angelis, Filippo
;
2012
Abstract
A new general synthetic access to carboxylated quaterpyridines (qpy), of interest as ligands for panchromatic dye-sensitized solar cell organometallic sensitizers, is presented. The strategic step is a Suzuki-Miyaura cross-coupling reaction, which has allowed the preparation of a number of representative unsubstituted and alkyl and (hetero)aromatic substituted qpys. To bypass the poor inherent stability of 2-pyridylboronic acid derivatives, we successfully applied N-methyliminodiacetic acid (MIDA) boronates as key reagents, obtaining the qpy ligands in good yields up to (quasi)gram quantities. The structural, spectroscopic (NMR and UV-vis), electrochemical, and electronic characteristics of the qpy have been experimentally and computationally (DFT) investigated. The easy access to the bis-thiocyanato Ru(II) complex of the parent species of the qpy series, through an efficient route which bypasses the use of Sephadex column chromatography, is shown. The bis-thiocyanato Ru(II) complex has been spectroscopically (NMR and UV-vis), electrochemically, and computationally investigated, relating its properties to those of previously reported Ru(II)-qpy complexes.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
