异氰化物与取代基相关的叠氮化物加成产生强发光的铱络合物,Journal of the American Chemical Society

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异氰化物与取代基相关的叠氮化物加成产生强发光的铱络合物
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-05 , DOI: 10.1021/jacs.2c11062
Chenggang Jiang ₁ , Louise M Cañada ₁ , Ngoc Bao Nguyen ₁ , Michael D S Halamicek ₁ , Sami H Nguyen ₁ , Thomas S Teets ₁

Affiliation

以配体为中心的功能化反应提供了多种策略来制备发光有机金属化合物。这些化合物可以具有传统配位化学无法获得的独特结构，并且可以具有增强的或不寻常的光物理特性。在这里，我们表明双环金属化铱双异氰化物配合物 ( 1 ) 与叠氮化物 (N ₃^– ) 反应形成新型发光结构。与叠氮化物反应的结果主要取决于芳基异氰化物上的取代基。具有吸电子取代基（CF ₃或 NO ₂）的那些与 1 当量的叠氮化物反应，然后通过 N ₂挤出，形成芳基氰氨基产物 ( 2). 对于芳基异氰化物上的供电子基团，反应性更加多样化，并且可能出现三种结果。在两种情况下，异氰化物和叠氮化物会发生 [3 + 2] 环加成反应，形成C结合的四氮唑结构 ( 3 )。在其他三种情况下，2 当量的叠氮化物参与了以前未观察到的结构的形成，其中四唑基和芳基氨基氰基偶联并重排以形成由 N 键四唑基和无环二氨基卡宾 (4) 组成的螯合配体。最后，双金属芳基氨基氰络合物 ( 5) 在一种情况下是孤立的。所有化合物都是发光的，一些化合物在溶液中具有出色的光致发光量子产率，天蓝色发射高达 0.81，黄色发射为 0.87，聚合物薄膜中橙红色发射为 0.65。

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Substituent-Dependent Azide Addition to Isocyanides Generates Strongly Luminescent Iridium Complexes

Ligand-centered functionalization reactions offer diverse strategies to prepare luminescent organometallic compounds. These compounds can have unique structures that are not accessible via traditional coordination chemistry and can possess enhanced or unusual photophysical properties. Here we show that bis-cyclometalated iridium bis-isocyanide complexes (1) react with azide (N₃^–) to form novel luminescent structures. The fate of the reaction with azide is determined primarily by the substituent on the aryl isocyanide. Those with electron-withdrawing substituents (CF₃ or NO₂) react with 1 equiv of azide followed by N₂ extrusion, forming aryl cyanamido products (2). With electron-donating groups on the aryl isocyanide the reactivity is more diverse, and three outcomes are possible. In two cases, the isocyanide and azide undergo a [3 + 2] cycloaddition to form a C-bound tetrazolato structure (3). In three other cases, 2 equiv of azide are involved in the formation of a previously unobserved structure, where a tetrazolato and aryl cyanamido couple and rearrange to form a chelating ligand comprised of an N-bound tetrazolato and an acyclic diaminocarbene (4). Finally, a bimetallic aryl cyanamido complex (5) is isolated in one case. All compounds are luminescent, some with exceptional photoluminescence quantum yields as high as 0.81 in solution for sky-blue emission, and 0.87 for yellow emission and 0.65 for orange-red emission in polymer films.

更新日期：2023-01-05

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