Synthesis of Re(I) Rings Comprising Different Re(I) Units and Their Light-Harvesting Abilities
Synthesis of Re(I) Rings Comprising Different Re(I) Units and Their Light-Harvesting Abilities
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不同Re(I)单元的Re(I)环的合成及其光捕获能力
DOI：
10.1021/acs.inorgchem.8b02421
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发表时间：
2018
影响因子：
4.6
通讯作者：
Ishitani Osamu
中科院分区：
文献类型：
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作者：
Yamazaki Yasuomi;Rohacova Jana;Ohtsu Hiroyoshi;Kawano Masaki;Ishitani Osamu
N-氧化三甲胺（Me_3NO）能选择性地脱除fac-[Re（N ^N）（CO）_3（PR_2R ′）]~+（N ^N =二亚胺配体）中的一个CO配体，从而只脱除转座到磷配体上的CO配体，以较好的产率得到顺式，trans-[Re I（N ^N）（CO）_2（PR_2R ′）（L）]_n~+。发现使用Me3NO的这种脱羰基反应对于合成在二亚胺配体中具有吸电子基团的双羰基Re（I）配合物特别有用，所述配合物不能通过光化学方法合成或仅以低产率获得。Me3NO还能选择性地将具有fac-[Re（N ^N）（CO）3（PR2R ′）]+结构的Re（I）多核配合物边缘单元中的羰基配体转位为磷配体。该反应成功地应用于合成一种新型的前体与环状多核配合物（Re环）包含不同类型的Re（I）单元。新合成的Re环由一个含4，4 ′-二（三氟甲基）-2，2 ′-联吡啶（CF3bpy）配体的Re单元和一个或两个含2，2 ′-联吡啶（bpy）配体的Re单元组成，从含bpy的Re单元到含CF3bpy的Re单元，表现出几乎定量的激发能收集能力.
TrimethylamineN-oxide (Me3NO) could selectively remove only one CO ligand fromfac-[Re(N^N)(CO)3(PR2R′)]+(N^N = diimine ligand), whereby only the CO ligand in thetransposition to the phosphorus ligand was selectively removed to givecis,trans-[ReI(N^N)(CO)2(PR2R′)(L)]n+in good yields. This decarbonylation reaction using Me3NO was found to be especially useful for synthesizing biscarbonyl Re(I) complexes with electron-withdrawing groups in the diimine ligand, which could not be synthesized or were obtained only in low yields by the photochemical method. Me3NO also selectively removed the carbonyl ligands in thetransposition to the phosphorus ligands from the edge Re(I) complex units, which have thefac-[Re(N^N)(CO)3(PR2R′)]+structure, in linear-shaped Re(I) multinuclear complexes. This reaction was successfully applied to synthesize a novel precursor with ring-shaped multinuclear Re complexes (Re-rings) comprising different kinds of Re(I) units. The newly synthesized Re-rings, which consist of one Re unit with a 4,4′-bis(trifluoromethyl)-2,2′-bipyridine (CF3bpy) ligand and one or two Re unit(s) with a 2,2′-bipyridine (bpy) ligand, showed almost quantitative excitation-energy harvesting ability from the Re unit(s) with bpy to that with CF3bpy.