A Rational Protocol for the Synthesis of Arylated Bipyridine Ligands via a Cycloaddition Pathway

A generic design principle for the preparation of a variety of substituted phenyl−polypyridine ligands is
described. These ligands are readily prepared by a regioselective [4+2] cycloaddition between electron-deficient dienes, such as 2,6-disubstituted-1,3,4-triazines, and ethynyl−arenes or ethynyl−alkanes.
Exceptional reactivity is found with electron-rich dienophiles bearing ethynylgallate or ethynylphenyldibutylamino groups. Two regioisomers are formed, the meta being preferred due to favorable π−π
interactions in the transition state, while the para isomers are formed in low yields in most cases. The
use of tert-butylacetylene or N,N-dimethylamino-2-propyne, however, drives the reaction exclusively to
the para isomer. Di-N,N-dibutylaminophenyl or isoquinoline ligands can also be produced in a single
step by reverse Diels−Alder reactions. Cross-coupling reactions of iodo-substituted ligands or their
platinum(II) complexes under Pd(0) catalysis gives branched ligands and complexes bearing paraffin
chains, electron-donor or electron-acceptor groups. The use of a chloro−Pt(II) complex of an iodo-functionalized ligand allows both halogens to be replaced by ethynyl groups by using different catalysts.
This methodology readily accommodates various functional groups and has been successfully extended
to systems containing a variety of donor/acceptor frameworks. All ligands strongly absorb in the near-UV and luminesce in solution at rt with quantum yields ranging from 0 to 66%. Excited state lifetimes
are in the nanosecond range and the solvent effects are in keeping with singlet excited states mixed with
charge-transfer character. As deduced from spectroscopic and electrochemical studies, the di-n-butylamino
derivatives are strong reductants in the excited state.