当前位置：
X-MOL 学术
›
Organometallics
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Dual-Emissive Bis(diphenylphosphino)amine Platinum Complexes: Structural, Reactivity, Photophysical, and Theoretical Investigations
Organometallics ( IF 2.5 ) Pub Date : 2020-08-25 , DOI: 10.1021/acs.organomet.0c00301 Mahboubeh Jamshidi 1, 2 , S. Reza Barzegar-Kiadehi 1 , Mohsen Golbon Haghighi 1 , Behrouz Notash 1
Organometallics ( IF 2.5 ) Pub Date : 2020-08-25 , DOI: 10.1021/acs.organomet.0c00301 Mahboubeh Jamshidi 1, 2 , S. Reza Barzegar-Kiadehi 1 , Mohsen Golbon Haghighi 1 , Behrouz Notash 1
Affiliation
|
By the reactions of bis(diphenylphosphino)amine (dppa) with equimolar amounts of cycloplatinated(II) complexes 1 with two neutral (SMe2 or DMSO) and anionic (Cl– or CF3CO2–) labile ligands the bis-chelate complexes 2 with a chelating mode of dppa were synthesized that have one of the smallest bite angles in a diphosphine. As the usual strategy for synthesizing the binuclear complexes, the reactions of 0.5 equiv of dppa with cycloplatinated(II) complexes 1 with a Cl– ligand were successful in making symmetrical binuclear complexes. Also, the chelating dppa has a strong angle strain that makes it a susceptible precursor for biphosphine ring opening. Furthermore, this new strategy was successful for designing symmetrical and unsymmetrical binuclear complexes with Cl– ligands. Interestingly, all efforts to make binuclear complexes with bridging dppa from precursors that contain CF3CO2– were unsuccessful by both strategies. The effects of dimerization via a change in the coordination mode of dppa, from a chelate mode in complexes 2 with green emission to a bridge mode in complexes 3, with dual-phosphorescence red emission were investigated in the powder and poly(methyl methacrylate) (PMMA) phases at 77 and 298 K. The emission decay curves of all complexes in the solid state show long and short lifetime values as characteristics of the triplet excited states. The reaction pathway, reactivity, and structural aspects of the complexes were compared with those of other similar dppm analogues and the mechanism of conversion via possible intermediates was considered by density functional theory (DFT) calculations. For interpretation of the emission spectra, time-dependent DFT (TD-DFT) calculations were carried out on the isolated and stacked forms.
中文翻译：
双发射双（二苯基膦基）胺铂配合物：结构，反应性，光物理和理论研究。
通过双用等摩尔量的环铂（II）的反应（二苯基膦基）胺（DPPA）络合物1具有两个中性（SME 2或DMSO）和阴离子（氯-或CF 3 CO 2 - ）不稳定配体的双-螯合络合物合成了具有dppa螯合模式的2个，其在二膦中具有最小的咬合角之一。作为合成的双核配合物的通常策略，与环铂0.5当量DPPA的的反应（II）配合物1被一个Cl -配体成功制备了对称的双核复合物。同样，螯合的dppa具有很强的角度应变，使其成为双膦开环的敏感前体。此外，这种新的策略是成功的设计对称和非对称的双核配合物氯-配体。有趣的是，所有的努力，使与包含CF桥接前体DPPA双核配合物3 CO 2 -是由这两种策略是不成功的。通过改变dppa的配位模式，从具有绿色发射的配合物2中的螯合模式到配合物3中的桥模式，可以实现二聚作用。分别在77和298 K的粉末和聚甲基丙烯酸甲酯（PMMA）相中研究了具有双磷光的红色发射。所有配合物在固态下的发射衰减曲线显示出长寿命和短寿命值是三重态的特征兴奋的状态。将复合物的反应途径，反应性和结构方面与其他类似的dppm类似物进行了比较，并通过密度泛函理论（DFT）计算来考虑通过可能的中间体的转化机理。为了解释发射光谱，对孤立和堆叠的形式进行了时变DFT（TD-DFT）计算。
更新日期：2020-09-14
中文翻译：
双发射双（二苯基膦基）胺铂配合物：结构，反应性，光物理和理论研究。
通过双用等摩尔量的环铂（II）的反应（二苯基膦基）胺（DPPA）络合物1具有两个中性（SME 2或DMSO）和阴离子（氯-或CF 3 CO 2 - ）不稳定配体的双-螯合络合物合成了具有dppa螯合模式的2个，其在二膦中具有最小的咬合角之一。作为合成的双核配合物的通常策略，与环铂0.5当量DPPA的的反应（II）配合物1被一个Cl -配体成功制备了对称的双核复合物。同样，螯合的dppa具有很强的角度应变，使其成为双膦开环的敏感前体。此外，这种新的策略是成功的设计对称和非对称的双核配合物氯-配体。有趣的是，所有的努力，使与包含CF桥接前体DPPA双核配合物3 CO 2 -是由这两种策略是不成功的。通过改变dppa的配位模式，从具有绿色发射的配合物2中的螯合模式到配合物3中的桥模式，可以实现二聚作用。分别在77和298 K的粉末和聚甲基丙烯酸甲酯（PMMA）相中研究了具有双磷光的红色发射。所有配合物在固态下的发射衰减曲线显示出长寿命和短寿命值是三重态的特征兴奋的状态。将复合物的反应途径，反应性和结构方面与其他类似的dppm类似物进行了比较，并通过密度泛函理论（DFT）计算来考虑通过可能的中间体的转化机理。为了解释发射光谱，对孤立和堆叠的形式进行了时变DFT（TD-DFT）计算。
京公网安备 11010802027423号