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Molecular and Nanoaggregation in Cyclometalated Iridium(III) Complexes through Structural Modification
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文摘
New terpyridyl ligands TP1, TP2 and cyclometalated iridium(III) complexes 1 and 2 based on these ligands have been synthesized. The ligands and complexes have been characterized by elemental analysis and spectroscopic studies (ESI-MS, 1H and 13C NMR, UV/Vis, fluorescence). The molecular structure of 1 has been verified by X-ray single-crystal analysis. It has been unambiguously established that variation of the substituents on 1 and 2 leads to molecular aggregation in 1, while 2 remains nonaggregated. Furthermore, complexes 1 and 2 have been successfully utilized as capping agents for the stabilization of gold nanoparticles (AuNPs). It is of note that 1 forms discretely, while 2 aggregates AuNPs through the assemblage of ultrasmall nanoparticles. It has been affirmed by 1H NMR titration studies that –NH groups from 1 and 2 are involved in the capping of AuNPs. The role of simple structural variations in directing molecular and nanoaggregation has been clearly established for the first time by spectroscopic (UV/Vis, fluorescence, 1H NMR titration) and morphological studies [SEM, TEM, EDX (energy-dispersive X-ray), DLS (dynamic light scattering)].

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