CAJ | 학술논문

采用密度泛函方法对两种Ir（ppy）2（O＾N）（ppy＝2-苯基吡啶；O＾N＝2-（2-羟基苯）-苯并噻唑（1）， O＾N＝2-（2-羟基苯）-苯并恶唑（2））配合物的几何结构和光谱特征进行了详细的理论研究。计算得到的Ir-N（1）、 Ir-N（3）和Ir-O（1）基态键长和相应实验值符合得较好。激发态下， Ir-N（1）和Ir-C（1）键长均增加了约0.02～0.05?，而Ir-O（1）键长则缩短了大约0.02?。在TD-DFT计算水平下结合极化连续介质（ PCM）模型，得到1～2的最低能吸收和发射分别出现在484 nm（1）、441 nm （2）和624 nm（1）、519 nm（2）。1和2的此跃迁均属于[d（Ir）＋π（ppy）＋π（O＾N）→π*（O＾N）]的电荷转移跃迁。计算结果表明， ppy和O＾N配体在跃迁过程中担当两个独立的发色团。与分子2相比，由于1在O＾N配体上存在噻唑环，导致其分子整体结构变化较大，并使吸收和发射波长产生明显红移。
채용밀도범함방법대량충Ir（ppy）2（O＾N）（ppy＝2-분기필정；O＾N＝2-（2-간기분）-분병새서（1）， O＾N＝2-（2-간기분）-분병악서（2））배합물적궤하결구화광보특정진행료상세적이론연구。계산득도적Ir-N（1）、 Ir-N（3）화Ir-O（1）기태건장화상응실험치부합득교호。격발태하， Ir-N（1）화Ir-C（1）건장균증가료약0.02～0.05?，이Ir-O（1）건장칙축단료대약0.02?。재TD-DFT계산수평하결합겁화련속개질（ PCM）모형，득도1～2적최저능흡수화발사분별출현재484 nm（1）、441 nm （2）화624 nm（1）、519 nm（2）。1화2적차약천균속우[d（Ir）＋π（ppy）＋π（O＾N）→π*（O＾N）]적전하전이약천。계산결과표명， ppy화O＾N배체재약천과정중담당량개독립적발색단。여분자2상비，유우1재O＾N배체상존재새서배，도치기분자정체결구변화교대，병사흡수화발사파장산생명현홍이。
The geometries and spectroscopic properties of a series of Ir (ppy)2(O^N)(ppy=2-phenylpyridine;O^N=2-(2-Hydroxyphenyl) -benzothiazole (1), O^N =2 -(2 -hydroxyphenyl) -benzoxazole (2)) were investigated theoretically.The calculated bond lengths of Ir-N(1), Ir-N(3) and Ir-O(1) in the ground state agreed well with the corresponding experimental results.Upon excitation, the bond lengths of Ir -N(1) and Ir-C(1) lengthen by 0.02~0.05 ?and that of Ir-O(1) shortened by 0.02?.At the TD-DFT level with the PCM model , 1~2 give rise to lowest -lying absorptions at 484(1), 441(2) nm and phosphorescent emissions at 624(1), 519(2) nm, respectively.The transitions of 1, 2 were attributed to [d(Ir)+π(ppy)+π(O^N)→π*(O^N)] charge transfer.The calculated results showed that the ppy and O^N groups acted as two independent chromospheres in transition processes.Compared with 2 , the geometric structure was greatly affected and the absorptions and emissions were red -shifted by benzothiazole groups on the O^N ligand of complexes 1.