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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Synthesis and photophysical studies of calix[4]arene-based binuclear platinum(II) complexes: Probing metal-metal and ligand-ligand interactions
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Synthesis and photophysical studies of calix[4]arene-based binuclear platinum(II) complexes: Probing metal-metal and ligand-ligand interactions

机译：杯[4]亚芳基双核铂（II）配合物的合成和光物理研究：探测金属-金属和配体-配体之间的相互作用

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摘要

A series of calix[4]arene-based binuclear platinum(II) complexes, Pt2LCl2 (1, L = 5,11,17,23-tetra-tert-butyl-25,27-di[methoxy(4-phenyl)-(C boolean AND N boolean AND N)]-26,28-dihydroxycalix[4]arene, HC boolean AND N boolean AND N = 6-phenyl-2,2'-bipyridine), [Pt2L(mu-dppC(n))]-(ClO4)(2) (dppC(n) = bis(diphenylphosphino)-methane (2, n = 1), -ethane (3, n = 2), -propane (4, n = 3), and [Pt2L(PPh3)(2)](ClO4)(2) (5), have been designed and synthesized in this work. Spectroscopic investigation demonstrates that p-tert-calix[4]arene is capable of assembling the two square-planar [(C boolean AND N boolean AND N)Pt(II)] units in a face-to-face manner, simultaneously suppressing intermolecular aggregation and increasing the solubility of the studied complexes. Facile replacement of the chloride ligand in 1 by the strongly a-donating ancillary phosphine ligands affords binuclear platinum(11) complexes with improved photophysical properties. All of the complexes are emissive both in the fluid/glassy solution and in the solid state, except for 1 in the solid state at room temperature. Moreover, the absorption and emission energies of the complexes are sensitive to the ancillary ligands. Varying the tethered phosphine auxiliaries from dppm (2) and dppe (3) to dppp (4) and PPh3 (5) modulates the intramolecular metal-metal (Pt center dot center dot center dot Pt) and ligand-ligand (pi-pi) distances, thereby leading to a switch of (MMLCT)-M-3 and excimeric (3)(pi pi*) excited states to a common (MLCT)-M-3 excited state.
机译：一系列基于杯[4]芳烃的双核铂（II）配合物Pt2LCl2（1，L = 5,11,17,23-四叔丁基-25,27-二[甲氧基（4-苯基）- （C布尔AND N布尔AND N）]-26,28-二羟基杯[4]芳烃，HC布尔AND N布尔AND N = 6-苯基-2,2'-联吡啶），[Pt2L（mu-dppC（n） ）]-（ClO4）（2）（dppC（n）=双（二苯基膦基）-甲烷（2，n = 1），-乙烷（3，n = 2），-丙烷（4，n = 3）和[Pt2L（PPh3）（2）]（ClO4）（2）（5）已设计并合成，光谱研究表明，p-叔杯[4]芳烃能够组装两个正方形[（C boolean AND N boolean AND N）Pt（II）]单元以面对面的方式同时抑制分子间的聚集并提高了所研究配合物的溶解度。供体的辅助膦配体可提供具有改善的光物理性质的双核铂（11）配合物，所有配合物在液体/ gl中均具有发射性总成和固溶体溶液，室温下为1固溶体。此外，配合物的吸收和发射能量对辅助配体敏感。从dppm（2）和dppe（3）到dppp（4）和PPh3（5）改变束缚的磷化氢辅助剂，以调节分子内金属-金属（Pt中心点中心点中心点中心点Pt）和配体-配体（pi-pi）距离，从而导致（MMLCT）-M-3和激基（3）（pi pi *）激发态转换为普通（MLCT）-M-3激发态。

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