Greenberg Matthew W, Tulloch Kris M, Reynoso Michelle E, Knapp Juliette L, Sayem Farman H, Bartkus Daphne D, Lum Ryan H, LaFratta Christopher N, Tanski Joseph M, Anderson Craig M
Department of Chemistry & Biochemistry, Bard College, 30 Campus Road,Annandale-on-Hudson, New York 12504, United States.
Department of Chemistry, Vassar College, Poughkeepsie, New York 12604, United States.
ACS Omega. 2023 Oct 6;8(41):38587-38596. doi: 10.1021/acsomega.3c05567. eCollection 2023 Oct 17.
Platinum(II) and platinum(IV) compounds were prepared by the stereoselective and regioselective reactions of thiophene-derived cyclohexyl diimine C^N^N-ligands with [PtMe(μ-SMe)]. Newly synthesized ligands were characterized by NMR spectroscopy and elemental analysis, and Pt(II)/Pt(IV) compounds were characterized by NMR spectroscopy, elemental analysis, high-resolution mass spectrometry, and single-crystal X-ray diffraction. UV-vis absorbance and photoluminescence measurements were performed on newly synthesized complexes, as well as structurally related Pt(II)/Pt(IV) compounds with benzene-derived cyclohexyl diimine ligands, in dichloromethane solution, as solids, and as 5% by weight PMMA-doped films. DFT and TD-DFT calculations were performed, and the results were compared with the observed spectroscopic properties of the newly synthesized complexes. X-ray total scattering measurements and real space pair distribution function analysis were performed on the synthesized complexes to examine the local- and intermediate-range atomic structures of the emissive solid states.
通过噻吩衍生的环己基二亚胺C^N^N配体与[PtMe(μ-SMe)]的立体选择性和区域选择性反应制备了铂(II)和铂(IV)化合物。通过核磁共振光谱和元素分析对新合成的配体进行了表征，通过核磁共振光谱、元素分析、高分辨率质谱和单晶X射线衍射对铂(II)/铂(IV)化合物进行了表征。对新合成的配合物以及具有苯衍生的环己基二亚胺配体的结构相关的铂(II)/铂(IV)化合物，在二氯甲烷溶液、固体状态以及5%重量的聚甲基丙烯酸甲酯掺杂薄膜中进行了紫外可见吸收和光致发光测量。进行了密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)计算，并将结果与新合成配合物的观测光谱性质进行了比较。对合成的配合物进行了X射线全散射测量和实空间对分布函数分析，以研究发光固态的局部和中程原子结构。
