摘要
采用MP2和CIS方法分别优化trans-[M2(CN)4(PH2CH2PH2)2][M=Pt(1),Pd(2)和Ni(3)]和trans-[M(CN)2(PH3)2][M=Pt(4),Pd(5)和Ni(6)]的基态和1,3[2(dz)(pz)]激发态结构.CIS计算显示1的激发态Pt-Pt距离相对基态变短,而2和3的金属间距离却增长.TD-DFT方法合理地预测了1～6发射能,如:1在CH2Cl2溶液中分别拥有348和404nm的荧光和磷光发射,与实验的386和448nm相对应.在1～3的激发态中,d8-d8相互作用依次递减,相应的发射跃迁能增加;与单核配合物4～6相比,金属间相互作用使得双核Pt配合物的发射波长红移,而对双核Pd和Ni配合物影响很小.
The structures of trans-[M2（CN）4（PH2CH2PH2）2] [M=Pt （1）, Pd （2） and Ni （3）] and trans- [M（CN）2（PH3）2] [M=Pt （4）, Pd （5） and Ni （6）] in the ground and 1,3[ （dz2） （Pz）] excited states were optimized by the MP2 and CIS methods, respectively. The CIS calculations revealed that upon excitation the Pt-Pt distance of 1 shortens but those of 2 and 3 lengthened. Experimental emissions were well reproduced by the TD-DFT calculations. For example, the fluorescent/phosphorescent emissions of I were predicted to take place at 356/417 nm in the solid state and at 348/404 nm in the CH2Cl2 solution, agreeing with experimental 388/450 and 386/448 nm, respectively. It is shown that the metal-metal interaction decreases on going from 1 to 3 in their excited states, leading to the increase of the σ（pz）→σ（dz^2） emission energy along the series complexes. With respect to analogous mononuclear d8 complexes （4-6）, the d^8-d^8 interaction results in a large red shift of emission wavelength for the binuclear Pt（Ⅱ） complex but slightly affects those of the binuclear Pd（Ⅱ） and Ni（Ⅱ） complexes.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2007年第11期1027-1031,共5页
Acta Chimica Sinica
基金
国家自然科学基金(Nos.20173021
20431030
20573042
20671032)
黑龙江省自然科学基金(No.B200601)
黑龙江大学杰出青年基金(No.JC2006L2)
黑龙江省博士后基金(No.LBH-Z06143)资助项目.
作者简介
E-mail：fuhg@vip．sina．com；Tel．：0451-86608545．
