【作者】 赵乐；

【导师】 任咏华； 吴立新；

【作者基本信息】 吉林大学 ， 物理化学， 2010， 博士

【摘要】 过渡金属Pt(II)具有d8电子构型,容易形成平面四方形配合物。由于金属-金属间相互作用力和分子内/分子间配体π–π相互作用的存在,这些配合物往往展现出一些特殊的光物理性质。乙炔基是很好的σ给电子体,它的引入大大增强了配体场的场强,减弱了MLCT态通过d-d态的失活,最终得到长寿命高量子产率的发光配合物。多金属氧簇化学组成丰富,拓扑结构多样,具有丰富的物理化学性质。两亲性分子在指导多金属氧簇的超分子自组装方面具有其独特的优势,表现出了很大的灵活性。在本论文中,我们设计合成了新的具有两亲性的Pt(II)配合物,并对其LB成膜性及包埋多金属氧簇形成复合物进行了研究。我们合成出一系列含有2,6-二(1′-烷基-3′-吡唑基)吡啶(N5Cn)的Pt(II)配合物[Pt(N5Cn)Cl]X (1–9)和[Pt(N5Cn)(C≡CR)]X (10–13) (X=三氟磺酸根或六氟磷酸根, R = C6H5, C6H4-CF3?p, C6H4-N(C6H5)2?p)。我们对这些Pt(II)配合物的氧化还原和光物理性质进行了研究。通过单晶X-射线衍射分析确定了几个Pt(II)配合物的分子结构。带有长烷基链的Pt(II)配合物[Pt(N5C14)Cl]PF6 (7)和[Pt(N5C14) (C≡CC6H5)]PF6 (13)能够在空气/水界面上形成有序、均一的单层膜。通过压力-面积等温(π-A)曲线,紫外-可见光光谱(UV-Vis),小角X-射线衍射(XRD),红外光谱(IR),偏振红外光谱(PIR),小角X-射线光电子能谱(XPS)等手段,我们对所得到的LB膜的结构与性质进行了详细的表征。我们还研究了Pt(II)配合物13多层膜的发光性质。我们利用Click反应,合成出一系列含有2,6-二(4′-1′,2′,3′-三氮唑基)吡啶(N7CR)的Pt(II)配合物[Pt(N7CR)Cl]X (1–7)和[Pt(N7CR)(C≡CR′)]X (8–13) (X=三氟磺酸根、六氟磷酸根或氯离子; R = CnH2n+1, C6H5, CH2C6H5; R′= C6H5, C6H4-CF3?p, C6H4-CF3?p, C6H4-N(CH3)2?p)。我们对这些Pt(II)配合物的氧化还原和光物理性质进行了研究。带有长烷基链的Pt(II)配合物[Pt(N7C12)Cl]Cl (3-Cl)和[Pt(N7C12)(C≡CC6H5)]Cl (13)能够在空气/水界面上形成有序、均一的单层膜。通过压力-面积等温(π-A)曲线,紫外-可见光光谱(UV-Vis),小角X-射线衍射(XRD),红外光谱(IR),偏振红外光谱(PIR)等手段,我们对所得到的LB膜的结构与性质进行了详细的表征。我们还研究了Pt(II)配合物13多层膜的发光性质。我们利用2,2′-联吡啶(bpy)和乙酰丙酮(acac)与Pt(II)配合,得到一系列新的Pt(II)配合物[Pt(bpy)(R-acac)]X (X=三氟磺酸根或六氟磷酸根; R = H或C12H25)。通过对乙酰丙酮3位上进行烷基取代(C12-acac),得到了带有长烷基链的两亲性Pt(II)配合物[Pt(bpy)(C12-acac)]PF6 (2)。我们对Pt(II)配合物(1和2)的光物理性质进行了研究。带有长烷基链的Pt(II)配合物(2)能够在空气/水界面上形成有序、均一的单层膜。通过压力-面积等温(π-A)曲线,紫外-可见光光谱(UV-Vis),小角X-射线衍射(XRD)等手段,我们对所得到的LB膜的结构与性质进行了基本的表征。我们还研究了Pt(II)配合物2多层膜的发光性质。我们尝试将带有正电荷的Pt(II)配合物( [Pt(N5C14)Cl]OTf和[Pt(N7C12)Cl]OTf),分别与Keggin型多金属氧簇磷钨酸(H3PW12O40)、硼钨酸钾(K9BW11O39)通过静电相互作用形成复合物(SEP1, SEP2),并对所得到复合物进行了基本表征。将复合物SEP2铺展在空气/水界面,得到了它的压力-面积等温(π-A)曲线。更多还原

【Abstract】 The third row transition metal platinum lies in Group 10 of the periodic table, and its most common oxidation state is +2 with d8 electronic configuration. Platinum(II) complexes usually adopt square planar geometry and they often exhibit intriguing spectroscopic and photophysical properties associated with the occurrence of Pt···Pt andπ?πinteractions. By the effect of the coordination of the stronglyσ-donating alkynyl ligand, the non-radiative deactivation via the d?d LF state can be reduced as a result of a larger d–d LF splitting. Thus, platinum(II) complexes with long lifetime and high quantum yield can be obtained. Polyoxometalates (POMs) exhibit abundant chemical composition, various topologies and extensive physical and chemical properties. Amphiphilic molecules possess special advantages for directing the supramolecular self-assembly of POMs, exhibiting considerable flexibility. In this dissertation, new classes of amphiphilic platinum(II) complexes have been designed and synthesized. In addition to their spectroscopic and luminescence properties, their Langmuir-Blodgett films and surfactant-encapsulated polyoxometalates (SEPs) have also been studied.Two series of novel platinum(II) 2,6-bis(1-alkyl-pyrazol-3-yl)pyridyl (N5Cn) complexes, [Pt(N5Cn)Cl]X (1?9) and [Pt(N5Cn)(C≡CR)]X (10?13) (X = OTf or PF6; R = C6H5, C6H4-CF3?p and C6H4-N(C6H5)2?p), with various chain length of alkyl groups on the nitrogen atom of pyrazolyl units have been successfully synthesized and characterized. Their electrochemical and photophysical properties have been studied. Some of their molecular structures have also been determined by X-ray crystallography. Two amphiphilic platinum(II) 2,6-bis(1-tetradecyl- pyrazol-3-yl)pyridyl (N5C14) complexes, [Pt(N5C14)Cl]PF6 (7) and [Pt(N5C14)(C≡CC6H5)]PF6 (13), were found to form stable and reproducible Langmuir films at the air-water interface. The characterization of such multilayer LB films has been investigated by the study of their surface pressure-area (π–A) isotherms, UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) and polarized IR spectroscopy. The luminescence property of 13 in Langmuir-Blodgett (LB) films has also been studied.Two series of novel platinum(II) 2,6-bis(1-alkyl-1,2,3-triazol-4-yl)pyridyl (N7R) complexes, [Pt(N7R)Cl]X (1?7) and [Pt(N7R)(C≡CR′)]X (8?13) (X = OTf or PF6; R = CnH2n+1, C6H5, CH2C6H5; R′= C6H5, C6H4-CF3?p, C6H4-CF3?p, C6H4-N(CH3)2?p), with various alkyl groups on the nitrogen atom of triazolyl units have been successfully synthesized and characterized. Their electrochemical and photophysical properties have been studied. Two amphiphilic platinum(II) 2,6-bis(1-dodecyl-1,2,3-triazol-4-yl)pyridyl (N7C12) complexes, [Pt(N7C12)Cl]Cl (3-Cl) and [Pt(N7C12)(C≡CC6H5)]Cl (13), were found to form stable and reproducible Langmuir films at the air-water interface. The characterization of such multilayer LB films has been investigated by the study of their surface pressure-area (π–A) isotherms, UV-vis spectroscopy, X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and polarized IR spectroscopy. The luminescence property of 13 in Langmuir-Blodgett (LB) films has also been studied.A series of novel platinum(II)(diimine)(acetylacetonate) ([Pt(bpy)(R-acac)]) complexes, [Pt(bpy)(R-acac)]X (1, 2) (X = OTf or PF6; R = CnH2n+1 or H), with various alkyl groups on the acac units has been successfully synthesized and characterized. Their photophysical properties have been studied. An amphiphilic platinum(II) complex, [Pt(bpy)(C12-acac)]PF6 (2) was found to form stable and reproducible Langmuir films at the air-water interface. The characterization of such multilayer LB films has been investigated by the study of their surface pressure-area (π–A) isotherms, UV-vis spectroscopy, X-ray diffraction (XRD). The luminescence property of 2 in Langmuir-Blodgett (LB) films has also been studied.Two SEPs of platinum(II) complexes ([Pt(N5C14)Cl]OTf and [Pt(N7C12)Cl]OTf) encapsulated Keggin type polyoxometalates (H3PW12O40 and K9BW11O39) (SEP1 and SEP2, respectively) have been successfully synthesized and characterized. The surface pressure-area (π–A) isotherm of SEP2 has also been investigated.更多还原