Reactivity and Luminescence Study of Platinum and Copper Complexes of 7-Azaindole Derivatives

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Zhao, Shu-Bin
C-H Activation , Luminescence , 7-Azaindole , Pt(II) Complex , Cu(I) Complex , Phosphorscence
The objective of this thesis is to explore new reactivities and to improve luminescent properties of 7-azaindole-containing metal complexes. Selectivity for the activation of toluene and ethyl benzene has been investigated with two cationic Pt(II)(N,N-L) complexes, where N,N-L = 1,2-bis(1-N-7-azaindolyl)benzene (BAB) or bis(1-N-7-azaindolyl)methane (BAM). A high regioselectivity toward toluene and ethyl benzene benzylic C-H activation and a distinct diastereoselectivity for ethyl benzene benzylic C-H activation are demonstrated. Detailed mechanistic studies have been performed, leading to the establishment of both the intermediacy of the η3-benzylic Pt(II) complexes in the reactions and the ligand steric impacts as origins for the distinct diastereoselectivity. A PtMe2 complex of 1-N-(pyridin-2-yl)-7-azaindole (NPA) has been synthesized and found to undergo facile transformation at ambient temperature, resulting in the quantitive formation of a neutral Pt4 molecular square. The mechanism of the transformation process has been examined, establishing a distinct intramolecular C-H driven self-assembly process. The geometrical impacts of the BAB and BAM ligands on the structure and stability of their fac-Pt(IV)Me3 complexes has been investigated. The BAB ligand is more effective than the BAM ligand in stabilizing the five-coordinate Pt(IV)Me3 complexes. With the BAB ligand, a five-coordinate fac-Pt(IV)Me3 complex is obtained; with the BAM ligand, two six-coordinate fac-Pt(IV)Me3 complexes are obtained. In solution, the methyl groups in the BAB complex exchange slowly, but those in the BAM complexes exchange rapidly. Several new 7-azaindolyl derivative ligands via either modifying or altering the BAM and BAB bridging groups have been developed. The syntheses, structures and reactivities of their Pt(II) complexes have been examined, leading to the finding of an unconventional C-Sn oxidative addition reaction. The modification of the NPA ligand via the incorporation of a triarylboron group has been carried out. Several novel Pt(II) and Cu(I) complexes have been synthesized and studied. A Cu(I) complex is found to display exceptionally bright ambient temperature phosphorescence. A series of dinuclear Cu(I) compounds of the 1,2,3,4-tetra(1-N-7-azaindolyl)benzene (TTAB) ligand have been synthesized and examined. The close contacts between the TTAB bridging phenyl ring and the Cu(I) centers are present in the complexes.
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