Azadipyrromethene-Based Near-Infrared Dyes: Effect of Thienylethynyl Substitution at the Distal and Proximal Phenyl Groups
Azadipyrromethene-Based Near-Infrared Dyes: Effect of Thienylethynyl Substitution at the Distal and Proximal Phenyl Groups
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DOI：
10.1002/ejic.201500348
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发表时间：
2015-08-01
影响因子：
2.3
通讯作者：
Sauve, Genevieve
中科院分区：
文献类型：
--
作者：
Daddario, Cassie M.;Han, Qi;Sauve, Genevieve
合成并表征了末端苯基H（CD 1）和近端苯基H（CD 2）上分别被噻吩乙炔基取代的氮杂二吡咯亚甲基（ADP）配体。噻吩基在第三位具有己基以改善在有机溶剂中的溶解度并防止乙炔基噻吩反应物的同偶联。为了进一步调节光电性质，取代的ADP与BF 2+和Zn-II配位。吸收光谱表明，噻吩乙炔基取代使染料的吸收光谱发生红移，当取代基被添加到邻近的苯基基团上时，位移更大。循环伏安实验表明，取代稳定的阴离子和二价阴离子。修饰配体（或锌螯合物）的还原电位不受噻吩乙炔基的位置的影响。新分子与聚（3-己基噻吩）（P3 HT）的共混物的初步研究表明，锌（II）螯合物具有作为有机太阳能电池的电子受体的潜力。
Azadipyrromethene (ADP) ligands substituted with thienylethynyl substituents either at the distal phenyl groups H(CD1) or the proximal phenyl groups H(CD2) were synthesized and characterized. The thienyl groups have a hexyl group at the third position to improve solubility in organic solvents and prevent homocoupling of the ethynylthiophene reactants. To further tune the opto-electronic properties, the substituted ADPs were coordinated with BF2+ and Zn-II. Absorption spectroscopy shows that the thienylethynyl substitutions redshift the absorption spectra of the dyes, with a larger shift when the substituents are added on the proximal phenyl groups. Cyclic voltammetry experiments show that the substitutions stabilize the anion and dianion. The reduction potentials for the modified ligands (or zinc chelates) were not affected by the placement of the thienylethynyl groups. Preliminary studies of blends of the new molecules with poly(3-hexylthiophene) (P3HT) suggest that the zinc(II) chelates have potential as electron acceptors for organic solar cells.