FACIAL TRIS CYCLOMETALATED RH3+ AND IR3+ COMPLEXES - THEIR SYNTHESIS, STRUCTURE, AND OPTICAL SPECTROSCOPIC PROPERTIES
FACIAL TRIS CYCLOMETALATED RH3+ AND IR3+ COMPLEXES - THEIR SYNTHESIS, STRUCTURE, AND OPTICAL SPECTROSCOPIC PROPERTIES
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DOI：
10.1021/ic00081a024
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发表时间：
1994-02-02
影响因子：
4.6
通讯作者：
BURGI, HB
中科院分区：
文献类型：
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作者：
COLOMBO, MG;BRUNOLD, TC;BURGI, HB
用广义方法合成了表面三环金属化配合物fac-[Rh(ppy)(3)] （ppyH = 2-苯基吡啶）、fac-[Ir(ppy)(3)]和fac-[Ir(thpy)(3)] （thpyH = 2-（2-噻吩基）吡啶）。在H-1核磁共振谱的基础上讨论了配合物的构象，得到了fac- [Ir(thpy)(3)]的室温晶体结构：化学式C27H18N3S3Ir，立方，空间群Fag， Z = 8, a = 16.872(4)埃a， V = 4803(3)埃a(3)。利用吸收光谱、发光光谱和发光线窄化光谱研究了不同介质下的激发态特性。在聚甲基丙烯酸甲酯（PMMA）中嵌入的fac-[(Rh(ppy)(3)]和fac-[Ir(thpy)(3)]的最低激发态分别对应于配体中心的3 pi-pi*跃迁，分别位于21 500和18 340 cm（-1）处，而对于fac-[Ir(ppy)，发现了金属到配体的电荷转移（(3)MLCT）的最低激发态。在(3)π - π(*)最低激发态中混合电荷转移特征的证据是由较短的发光衰减时间提供的。
The synthesis of the facial tris cyclometalated complexes fac-[Rh(ppy)(3)] (ppyH = 2-phenylpyridine), fac-[Ir(ppy)(3)], and fac-[Ir(thpy)(3)] (thpyH = 2-(2-thienyl)pyridine) by a generalized method is described. The conformation of the complexes is discussed on the basis of the H-1 NMR spectra, and for fac- [Ir(thpy)(3)] the room-temperature crystal structure is presented: chemical formula C27H18N3S3Ir, cubic, space group Fag, Z = 8, a = 16.872(4) Angstrom A., V = 4803(3) Angstrom A(3). The-excited-state properties are investigated by absorption, luminescence, and luminescence line-narrowing spectroscopy in different media. The lowest excited states of fac-[(Rh(ppy)(3)] and fac-[Ir(thpy)(3)] embedded in poly(methyl methacrylate) (PMMA) correspond to ligand-centered 3 pi-pi* transitions at 21 500 and 18 340 cm(-1), respectively, whereas for fac-[Ir(ppy),l a metal to ligand charge-transfer ((3)MLCT) lowest excited state is found. Evidence for a mixing of charge-transfer character into the (3) pi-pi(*) lowest excited states is provided by the short luminescence decay times.