State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter and Graduate School of CAS, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Inorg Chem. 2010 Mar 1;49(5):2210-21. doi: 10.1021/ic902019s.
Reactions of 1,3-bis(2-pyridylimino)isoindoline (HL1), 1,3-bis(2-pyridylimino)benz(f)isoindoline (HL2), or 5,6-dihydro-2,3-diphenyl-5-(pyridin-2-ylimino)pyrrolo[3,4-b]pyrazin-7-ylidene)pyridin-2-amine (HL3) with Pt(tht)(2)Cl(2) (tht = tetrahydrothiophene) afforded the corresponding Pt(L)Cl complexes. A series of neutral platinum(II) alkynyl complexes Pt(L)(C[triple bond]CR) were prepared by reactions of the precursors Pt(L)Cl with alkynyl ligands through CuI-catalyzed platinum acetylide sigma coordination. Crystal structural determination of Pt(L3)Cl (3), Pt(L1)(C[triple bond]CPh) (4), and Pt(L1)(C[triple bond]CC(6)H(4)Bu(t)-4) (6) by X-ray crystallography revealed that the neutral platinum(Pi) complexes with monoanionic tridentate L ligands display more perfect square-planar geometry than that in platinum(II) complexes with neutral tridentate 2,2':6',2''-terpyridyl ligands. Both the Pt(L)Cl and Pt(L)(C[triple bond]CC(6)H(4)R-4) complexes exhibit low-energy absorption at 400-550 nm, arising primarily from pi --> pi*(L) intraligand (IL) and 5d(Pt) --> pi*(L) metal-to-ligand charge-transfer (MLCT) transitions as suggested from density functional theory calculations. They display bright-orange to red room-temperature luminescence in fluid dichloromethane solutions with microsecond to submicrosecond ranges of emissive lifetimes and 0.03-3.79% quantum yields, originating mainly from (3)IL and (3)MLCT excited states. Compared with the emissive state in Pt(L)Cl complexes, substitution of the coordinated Cl with C[triple bond]CC(6)H(4)R-4 in Pt(L)(C[triple bond]CC(6)H(4)R-4) complexes induces an obviously enhanced contribution from the (3)[pi(C[triple bond]CC(6)H(4)R-4) --> pi*(L)] ligand-to-ligand charge-transfer (LLCT) triplet state. The photophysical properties can be finely tuned by modifying both the L and alkynyl ligands. The calculated absorption and emission spectra in dichloromethane coincide well with those measured in a fluid dichloromethane solution at ambient temperature.
1,3-双(2-吡啶亚氨基)异吲哚啉（HL1）、1,3-双(2-吡啶亚氨基)苯并（f）异吲哚啉（HL2）或 5,6-二氢-2,3-二苯基-5-(吡啶-2-亚氨基)吡咯并[3,4-b]吡嗪-7-亚基)吡啶-2-胺（HL3）与 Pt(tht)(2)Cl(2)（tht = 四氢噻吩）反应生成相应的 Pt(L)Cl 配合物。通过 CuI 催化的铂炔 sigma 配位，将前体 Pt(L)Cl 与炔烃配体反应，制备了一系列中性铂（II）炔基配合物 Pt(L)(C[三重键]CR)。通过 X 射线晶体学对 Pt(L3)Cl（3）、Pt(L1)(C[三重键]CPh）（4）和 Pt(L1)(C[三重键]CC(6)H(4)Bu(t)-4)（6）的晶体结构测定表明，带有单阴离子三齿 L 配体的中性铂（Pi）配合物具有比带有中性三齿 2,2':6',2''-三联吡啶配体的铂（II）配合物更完美的平面正方形几何形状。Pt(L)Cl 和 Pt(L)(C[三重键]CC(6)H(4)R-4)配合物均在 400-550nm 处表现出低能量吸收，主要归因于来自密度泛函理论计算的π-π*(L)内配位（IL）和 5d(Pt)→π*(L)金属-配体电荷转移（MLCT）跃迁。它们在流体二氯甲烷溶液中显示出亮橙色到红色的室温磷光，发射寿命在微秒到亚微秒范围内，量子产率为 0.03-3.79%，主要来自(3)IL 和(3)MLCT 激发态。与 Pt(L)Cl 配合物的发射态相比，在 Pt(L)(C[三重键]CC(6)H(4)R-4)配合物中用 C[三重键]CC(6)H(4)R-4 取代配位的 Cl 会明显增强来自(3)[π(C[三重键]CC(6)H(4)R-4)→π*(L)]配体-配体电荷转移（LLCT）三重态的贡献。通过修饰 L 和炔烃配体，可以精细调节光物理性质。在二氯甲烷中的计算吸收和发射光谱与在环境温度下在流体二氯甲烷溶液中测量的光谱吻合良好。
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