Phosphorescent complexes of {Mo6I8}4+ with triazolates: [2+3] cycloaddition of alkynes to [Mo6I8(N3)6]2-

被引：14
|
作者：
Mironova, Alina D. [1 ]
Mikhailov, Maksim A. [1 ]
Brylev, Konstantin A. [1 ,2 ]
Gushchin, Artem L. [1 ,2 ]
Sukhikh, Taisiya S. [1 ,2 ]
Sokolov, Maxim N. [1 ,2 ,3 ]
机构：
[1] Russian Acad Sci, Siberian Branch, Nikolaev Inst Inorgan Chem, 3 Acad Lavrentiev Ave, Novosibirsk 630090, Russia
[2] Novosibirsk State Univ, 2 Pirogova Str, Novosibirsk 630090, Russia
[3] Kazan Fed Univ, 18 Kremlyovskaya Str, Kazan 420008, Russia
来源：
NEW JOURNAL OF CHEMISTRY | 2020年 / 44卷 / 47期
基金：
俄罗斯科学基金会;
关键词：
RHENIUM CLUSTER COMPLEXES; OCTAHEDRAL HEXARHENIUM(III) COMPLEXES; EXCITED-STATE PROPERTIES; HEXANUCLEAR MOLYBDENUM; SUPRAMOLECULAR ASSEMBLIES; PHOTOPHYSICAL PROPERTIES; IODIDE CLUSTER; LUMINESCENCE; AZIDES; REDOX;
D O I：
10.1039/d0nj04259e
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
(Bu4N)(2)[Mo6I8(N-3)(6)], prepared in a clean high-yield reaction from (Bu4N)(2)[Mo6I8(CH3COO)(6)] and Me3SiN3, undergoes [3+2] cycloaddition with CH3O(O)CC(O)OCH3 with the formation of a novel hexakis(triazolate) complex, (Bu4N)(2)[Mo6I8(N3C2(COOCH3)(2))(6)] with symmetrically coordinated 4,5-di(carbmethoxy)triazol-2-yl ligands. The product was characterized by X-ray analysis, NMR, IR and ESI-mass spectrometry. It undergoes a quasi reversible oxidation in CH3CN at E-1/2 = 1.36 V (vs. Ag/AgCl) and is red-light emissive upon UV photoexcitation. Reaction with methylpropiolate also yields a corresponding hexakis(triazolate) complex, [Mo6I8(N3C2H(COOCH3))(6)](2-), which exists as a 1 : 1 mixture of two isomers. Alkynes that lacking strongly electron-withdrawing substituents fail to undergo the cycloaddition reaction.
引用
收藏
页码：20620 / 20625
页数：6
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