Structural Modification on Copper(I)-pyridylpyrimidine Complexes for Modulation of Rotational Dynamics, Redox Properties, and Phototriggered Isomerization
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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)(LMes)]BF4 (1·BF4, Mepypm = 4-methyl-2-(2′-pyridyl)pyrimidine, LMes = 2,9-dimesityl-1,10-phenanthroline) was compared with previously reported complexes of [Cu(MepmMepy)(LMes)]BF4 (2·BF4, MepmMepy = 4-methyl-2-(6′-methyl-2′-pyridyl)pyrimidine), Cu(Mepypm)(DPEphos)]BF4 (3·BF4, DPEphos = bis[2-(diphenylphosphino)phenyl]ether), [Cu(Mepypm)(LAnth)]BF4 (4·BF4, LAnth = 2,9-bis(9-anthryl)-1,10-phenanthroline), and [Cu(Mepypm)(LMacro)]BF4 (5·BF4). 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.
