Oligomeric ligands incorporating multiple 5,5'-diethynyl-2,2'-bipyridine moieties bridged and end-capped by 3,4-dibutylthiophene units.
In this work, we detail the synthesis and photophysical properties of a series of soluble polybipyridine ligands comprising one to five bipyridine units sandwiched between rigid carbon-carbon triple bonds substituted by 3,4-dibutylthiophene repeating units. The dual Sonogashira coupling reaction of 5,5'-dibromo-2,2'-bipyridine with TMS- and (CH3)2C(OH)-protected acetylene allows the synthesis of a dissymmetrically functionalized building block which was selectively deprotected at either the TMS or 2-hydroxyprop-2-yl site. Various combinations allow the interconnection of the terminal alkyne to 3,4-dibutyl-2,5-diiodothiophene or 3,4-dibutyl-2-iodothiophene leading to bipyridine frameworks bearing two acetylene-protected groups or one acetylenethiophene/one acetylene-protected function. It is possible therefore to construct dimeric to pentameric bipyridine ligands where the chelating subunit is bridged by a 3,4-dibutyl-2,5-diethynylthiophene spacer and end-capped by a 3,4-dibutyl-2-ethynylthiophene stopper. All cross-coupling reactions are promoted with palladium(0) tetrakistriphenylphosphine under mild conditions. Spectroscopic data for the new oligomers are discussed in terms of the extent of pi-electron conjugation. Upon increasing the number of pi-electrons from 24 to 104, there is a progressive lowering in the energy of absorption and fluorescence transitions, while the emission quantum yields remain essentially constant. The LUMO levels of these large molecules, estimated by cyclic voltammetry, lie in the range -3.06 to -3.18 eV.
Goeb
Sébastien
S
Laboratoire de Chimie Moléculaire, Ecole de Chimie, Polymères, Matériaux (ECPM), Université Louis Pasteur (ULP), 25 rue Becquerel, 67087 Strasbourg Cedex 02, France.
De Nicola
Antoinette
A
Ziessel
Raymond
R
D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry*; D000042:Absorption; D008024:Ligands; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010777:Photochemistry; D011725:Pyridines / Q000138:chemical synthesis / Q000737:chemistry*; D013876:Thiophenes / Q000138:chemical synthesis / Q000737:chemistry*; D014466:Ultraviolet Rays
C499742:3,4-dibutylthiophene; C499743:5,5'-diethynyl-2,2'-bipyridine; D008024:Ligands; D011725:Pyridines; D013876:Thiophenes; D015082:2,2'-Dipyridyl