Structural
Modification on Copper(I)-pyridylpyrimidine Complexes for Modulation
of Rotational Dynamics, Redox Properties, and Phototriggered Isomerization
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Abstract
The
redox properties of copper pyridylpyrimidine complexes, which undergo
linkage isomerism based on pyrimidine ring rotation, were compared
under different coordination environments. A newly synthesized compound,
[Cu(Mepypm)(L<sub>Mes</sub>)]BF<sub>4</sub> (<b>1</b>·BF<sub>4</sub>, Mepypm = 4-methyl-2-(2′-pyridyl)pyrimidine, L<sub>Mes</sub> = 2,9-dimesityl-1,10-phenanthroline) was compared with
previously reported complexes of [Cu(MepmMepy)(L<sub>Mes</sub>)]BF<sub>4</sub> (<b>2</b>·BF<sub>4</sub>, MepmMepy = 4-methyl-2-(6′-methyl-2′-pyridyl)pyrimidine),
Cu(Mepypm)(DPEphos)]BF<sub>4</sub> (<b>3</b>·BF<sub>4</sub>, DPEphos = bis[2-(diphenylphosphino)phenyl]ether), [Cu(Mepypm)(L<sub>Anth</sub>)]BF<sub>4</sub> (<b>4</b>·BF<sub>4</sub>, L<sub>Anth</sub> = 2,9-bis(9-anthryl)-1,10-phenanthroline), and [Cu(Mepypm)(L<sub>Macro</sub>)]BF<sub>4</sub> (<b>5</b>·BF<sub>4</sub>).
Isomer ratios, isomerization dynamics, redox properties, and photoelectron
conversion functions varied with the coordination structure. Methyl
substituents on the 6-position of the pyridine moiety increased steric
repulsion and contributed to quicker rotation, enhanced photoluminescence,
and increased photodriven rotational isomerization
