Willison Stuart A, Jude Hershel, Antonelli Ryan M, Rennekamp Jeffrey M, Eckert Nathan A, Krause Bauer Jeanette A, Connick William B
Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, Ohio 45221-0172, USA.
Inorg Chem. 2004 Apr 19;43(8):2548-55. doi: 10.1021/ic035066k.
Four platinum(II) cationic complexes were prepared with the mer-coordinating tridentate ligands 2,6-bis(N-pyrazolyl)pyridine (bpp) and 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine (bdmpp): [Pt(bpp)Cl]Cl.H(2)O; [Pt(bdmpp)Cl]Cl.H(2)O; Pt(bpp)(Ph); Pt(bdmpp)(Ph). The complexes were characterized by (1)H NMR spectroscopy, elemental analysis, and mass spectrometry, and the structures of the bpp derivatives were determined by X-ray crystallography. [Pt(bpp)Cl]Cl.2H(2)O: monoclinic, P2(1)/n, a = 11.3218(5) A, b = 6.7716(3) A, c = 20.6501(6) A, beta = 105.883(2) degrees, V = 1522.73(11) A(3), Z = 4. The square planar cations stack in a head-to-tail fashion to form a linear chain structure with alternating Pt...Pt distances of 3.39 and 3.41 A. Pt(bpp)(Ph).CH(3)CN: triclinic, P, a = 8.3620(3) A, b = 10.7185(4) A, c = 13.4273(5) A, alpha = 96.057(1) degrees, beta = 104.175(1) degrees, gamma = 110.046(1) degrees, V = 1072.16(7) A(3), Z = 2. Cyclic voltammograms indicate all four complexes undergo irreversible reductions between -1.0 and -1.3 V vs Ag/AgCl (0.1 M TBAPF(6)/CH(3)CN), attributable to ligand- and/or metal-centered processes. By comparison to related 2,2':6',2' '-terpyridine complexes, the electrochemical and UV-visible absorption data are consistent with bpp being both a weaker sigma-donor and pi-acceptor than terpyridine. Solid samples of Pt(bpp)(Ph) at 77 K exhibit a remarkably intense, narrow emission centered at 655 nm, whereas the other three complexes exhibit only very weak emission.
使用mer-配位三齿配体2,6-双（N-吡唑基）吡啶（bpp）和2,6-双（3,5-二甲基-N-吡唑基）吡啶（bdmpp）制备了四种铂（II）阳离子配合物：[Pt（bpp）Cl]Cl·H₂O；[Pt（bdmpp）Cl]Cl·H₂O；Pt（bpp）（Ph）；Pt（bdmpp）（Ph）。通过¹H NMR光谱、元素分析和质谱对配合物进行了表征，并通过X射线晶体学确定了bpp衍生物的结构。[Pt（bpp）Cl]Cl·2H₂O：单斜晶系，P2₁/n，a = 11.3218(5) Å，b = 6.7716(3) Å，c = 20.6501(6) Å，β = 105.883(2)°，V = 1522.73(11) ų，Z = 4。平面正方形阳离子以头对尾的方式堆积形成线性链结构，Pt…Pt交替距离为3.39和3.41 Å。Pt（bpp）（Ph）·CH₃CN：三斜晶系，P，a = 8.3620(3) Å，b = 10.7185(4) Å，c = 13.4273(5) Å，α = 96.057(1)°，β = 104.175(1)°，γ = 110.046(1)°，V = 1072.16(7) ų，Z = 2。循环伏安图表明，所有四种配合物在相对于Ag/AgCl（0.1 M TBAPF₆/CH₃CN）的-1.0至-1.3 V之间经历不可逆还原，这归因于配体和/或金属中心过程。与相关的2,2':6',2''-三联吡啶配合物相比，电化学和紫外可见吸收数据表明bpp既是比三联吡啶更弱的σ供体，也是π受体。Pt（bpp）（Ph）的固体样品在77 K时在655 nm处表现出非常强烈、狭窄的发射，而其他三种配合物仅表现出非常微弱的发射。
