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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Dual emission from an iridium(III) complex/counter anion ion pair
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Dual emission from an iridium(III) complex/counter anion ion pair

机译：来自铱星（III）复合/计数A离子对的双重发射

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摘要

Ir(tpy)(2)](PF6)(3) (tpy = 2,2':6',2 ''-terpyridine) dissolved in CH3CN was found to exhibit dual color luminescent emission depending on the excitation wavelength. Specifically, blue and green emissions were obtained with excitation at 350 and 410 nm, respectively. Because the associated emission spectra were consistent with those of [Ir(tpy)(2)]Cl-3 in water and [Ir(tpy)(2)](PF6)(3) in the crystalline state, respectively, this dual emission is attributed to emissions from the [Ir(tpy)(2)](3+) cation and its ion pair [Ir(tpy)(2)](3+)center dot PF6-. The emission is assigned to the (3)pi-pi* transition of the ligands based on time-dependent density functional theory (TD-DFT) calculations. Conversely, [Ir(tpy)(2)]I-3 in CH3CN shows emission due to [Ir(tpy)(2)](3+) but not [Ir(tpy)(2)](3+)center dot I-, while crystalline [Ir(tpy)(2)]I-3 emits red luminescence at 77 K that is inconsistent with that from [Ir(tpy)(2)](3+). Since the emission energies of crystalline [Ir(tpy)(2)]X-3 (X- = Cl-, Br- or I-) show a good correlation with the electron affinity of X, the emissions are assigned to a counter anion to complex ion charge-transfer transition. This hypothesis is supported by TD-DFT calculations regarding [Ir(tpy)(2)](3+)center dot X-.
机译：研究发现，溶解在CH3CN中的Ir（tpy）（2）]（PF6）（3）（tpy=2,2'：6'，2'-三吡啶）根据激发波长表现出双色发光。具体来说，分别在350和410 nm的激发下获得蓝色和绿色发射。由于相关发射光谱分别与水中[Ir（tpy）（2）]Cl-3和结晶状态下[Ir（tpy）（2）]（PF6）（3）的发射光谱一致，这种双重发射归因于[Ir（tpy）（2）]（3+）阳离子及其离子对[Ir（tpy）（2）]（3+）中心点PF6-的发射。基于含时密度泛函理论（TD-DFT）计算，将发射分配给配体的（3）π-π*跃迁。相反地，CH3CN中的[Ir（tpy）（2）]I-3显示出由于[Ir（tpy）（2）]（3+）而不是[Ir（tpy）（2）]（3+）中心点I-而产生的发射，而晶体[Ir（tpy）（2）]I-3在77K下发射出与[Ir（tpy）（2）]（3+）不一致的红色发光。由于晶体[Ir（tpy）（2）]X-3（X-=Cl-、Br-或I-）的发射能量与X的电子亲和力表现出良好的相关性，因此发射被分配到反阴离子到复杂离子的电荷转移转变。这一假设得到了[Ir（tpy）（2）]（3+）中心点X-的TD-DFT计算的支持。

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    Ito Wataru; Hattori Shingo; Kondo Mio; Sakagami Hiroki; Kobayashi Osamu; Ishimoto Takayoshi; Shinozaki Kazuteru;

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    Yokohama City Univ Grad Sch Nanobiosci Dept Mat Sci Kanazawa Ku 22-2 Seto Yokohama Kanagawa 2360027 Japan;

    Yokohama City Univ Grad Sch Nanobiosci Dept Mat Sci Kanazawa Ku 22-2 Seto Yokohama Kanagawa 2360027 Japan;

    Yokohama City Univ Grad Sch Nanobiosci Dept Mat Sci Kanazawa Ku 22-2 Seto Yokohama Kanagawa 2360027 Japan;

    Yokohama City Univ Grad Sch Nanobiosci Dept Mat Sci Kanazawa Ku 22-2 Seto Yokohama Kanagawa 2360027 Japan;

    Yokohama City Univ Grad Sch Nanobiosci Dept Mat Sci Kanazawa Ku 22-2 Seto Yokohama Kanagawa 2360027 Japan;

    Yokohama City Univ Grad Sch Nanobiosci Dept Mat Sci Kanazawa Ku 22-2 Seto Yokohama Kanagawa 2360027 Japan;

    Yokohama City Univ Grad Sch Nanobiosci Dept Mat Sci Kanazawa Ku 22-2 Seto Yokohama Kanagawa 2360027 Japan;

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  • 正文语种 eng
  • 中图分类 化学;无机化学;
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