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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Photophysical,Spectroscopic,and Computational Studies of a Series of Re(I) Tricarbonyl Complexes Containing 2,6-Dimethylphenylisocyanide and 5- and 6-Derivatized Phenanthroline Ligands
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Photophysical,Spectroscopic,and Computational Studies of a Series of Re(I) Tricarbonyl Complexes Containing 2,6-Dimethylphenylisocyanide and 5- and 6-Derivatized Phenanthroline Ligands

机译：一系列含2,6-二甲基苯基异氰化物和5-和6-衍生的菲咯啉配体的Re（I）三羰基配合物的光物理，光谱和计算研究

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The ligand 2,6-dimethylphenylisocyanide (CNx) forms six complexes of the formula [Re(CO)_3(CNx)(L)]~+,where L=1,10-phenanthroline (1),5-chlbro-1,10-phenanthroline (2),5-nitro-1,10-phenanthroline (3),5-methyl-1,10-phenanthroline (4),5,6-dimethyl-1,10-phenanthroline (5),and 1,10-phenanthrolinopyrrole (6).The lowest-energy absorption peaks of the complexes red-shift in the order 1<2<3<4<5<6.The time-dependent density functional theory (TDDFT) and conductor-like polarizable continuum model (CPCM) computed singlet excited states in ethanol deviate by 1000 cm~(-1) or less from the experimental UV-vis peaks.The complexes undergo reversible reductions and irreversible oxidations.The electronic energy gap increases in the order 3<2<1<4<5<6,which is the order of increasing electron-donating power of the phen substituents.The reduction potentials linearly correlate with the B3LYP calculated LUMO energies for 1-6.The complexes emit at room temperature and at 77 K except 3,which emits only at 77 K.The calculated ~3MLLCT energies are within 1100 cm~(-1) from the experimental emission energies at 77 K.The 77 K emission curve-fitting analysis results agree with the computational assignment of the emitting state as ~3MLLCT for 1-5 and ~3LC for 6.The experimental 77 K emission energies and the calculated ~3MLLCT state energies increase in the order 6 < 5,3 < 2 < 4,1.The 77 K emission lifetimes increase upon addition of substituents from 65 mus for 1 to 171 mus for 2,to 230 mus for 4 and 5,and to 322 mus for 3.The emission quantum yields at room temperature in solution are 0.77,0.78,0.83,0.56,and 0.11 for complexes 1,2,4,5,and 6,respectively.
机译：配体2,6-二甲基苯基异氰化物（CNx）形成六种式[Re（CO）_3（CNx）（L）]〜+的配合物，其中L = 1,10-菲咯啉（1），5-chlbro-1， 10-菲咯啉（2），5-硝基-1,10-菲咯啉（3），5-甲基-1,10-菲咯啉（4），5,6-二甲基-1,10-菲咯啉（5）和1 ，10-菲咯啉吡咯（6）。配合物的最低能量吸收峰按1 <2 <3 <4 <5 <6的顺序红移。时变密度泛函理论（TDDFT）和导体似极化连续模型（CPCM）计算出乙醇中的单线激发态与实验UV-vis峰的偏差为1000 cm〜（-1）或更小，配合物发生可逆还原和不可逆氧化，电子能隙以3 <2的顺序增加<1 <4 <5 <6，这是phen取代基的供电子能力增加的顺序。还原电势与B3LYP计算的1-6的LUMO能量线性相关。配合物在室温和77 K下发射3除外，后者仅以77 K发射。计算出的〜3MLLCT能量在77 K时的实验发射能量的1100 cm〜（-1）以内.77 K发射曲线拟合分析结果与1-5和〜的发射态的〜3MLLCT的计算分配相符6的3LC。实验的77 K发射能量和计算出的〜3MLLCT状态能量按6 <5,3 <2 <4,1的顺序增加.77 K的发射寿命随着取代基的添加从65 mus持续1至171而增加2 mus到4和5的230 mus，3的322 mus。溶液在室温下的发射量子产率分别为0.77、0.78、0.83、0.56和1,2,4,5和0.11。 6，分别。

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