Komiya Naruyoshi, Okada Minoru, Fukumoto Kanako, Iwata Shotaro, Naota Takeshi
Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Toyonaka, Osaka 560-8531, Japan.
Dalton Trans. 2014 Jul 14;43(26):10074-85. doi: 10.1039/c4dt00560k. Epub 2014 May 29.
The synthesis, structure, and solid-state emission of vaulted trans-bis(salicylaldiminato)platinum(ii) complexes 1-3 with halogen functionalities are described and compared with the non-substituted analogues. Chloro-substitution provided an improvement of the low emission properties of short-vaulted, non-substituted complexes 1 and 2 in the crystalline state at ambient temperature, while the intense emission of long-vaulted analogues 3 remained unchanged. Bromo-substituted crystals also emit intensively, while the fluoro analogue is non-emissive under the same conditions. Temperature-dependent emission spectra indicate that all chloro- and bromo-substituted crystals with enhanced emission properties at ambient temperature exhibit improved heat resistance properties towards emission decay with the halogen functionalities. X-ray diffraction studies revealed that such a positive effect of halogenation for the enhancement of solid-state emission is due to significant molecular constraints in the crystals by a combination of the vaulted structure and three-dimensional HX hydrogen bonding interactions.
描述了具有卤素官能团的拱形反式双（水杨醛亚胺基）铂（II）配合物1-3的合成、结构和固态发射，并与未取代的类似物进行了比较。氯取代改善了短拱形、未取代配合物1和2在室温下晶体状态下的低发射性能，而长拱形类似物3的强发射保持不变。溴取代的晶体也强烈发射，而氟类似物在相同条件下不发射。温度依赖发射光谱表明，所有在室温下具有增强发射性能的氯和溴取代晶体，随着卤素官能团的存在，在发射衰减方面表现出改善的耐热性能。X射线衍射研究表明，卤化对增强固态发射的这种积极作用是由于拱形结构和三维HX氢键相互作用的结合，使晶体中存在显著的分子限制。
