Mixed-Ligand Organometallic Polymers Containing the "Pd2(dmb)22+" Fragment: Properties of the {Pd2(dmb)2(diphos)2+}n
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- 作者：Sté ; phanie Sicard ; Jean-Franç ; ois Bé ; rubé ; Dalila Samar ; Abdelhalim Messaoudi ; Daniel Fortin ; Fré ; dé ; ric Lebrun ; Jean-Franç ; ois Fortin ; Andreas Decken ; and P
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：August 23, 2004
- 年：2004
- 卷：43
- 期：17
- 页码：5321 - 5334
- 全文大小：339K
- 年卷期：v.43,no.17(August 23, 2004)
- ISSN：1520-510X
文摘
The 1:1 reaction between the d9-d9 Pd2(dmb)2Cl2 complex (dmb = 1,8-diisocyano-p-menthane) and the diphosphineligands (diphos) bis(diphenylphosphino)butane (5, dppb), bis(diphenylphosphino)pentane (6, dpppen), bis(diphenylphosphino)hexane (7, dpph), and bis(diphenylphosphino)acetylene (8, dpa) in the presence of LiClO4leads to the {[Pd2(dmb)2(diphos)](ClO4)2}n polymers. These new materials are characterized by NMR (1H, 13C,31P), IR, Raman, and UV-vis spectroscopies (466 < 
da.gif" BORDER=0 >max(d
-d*) < 480 nm), by ATG, XRD, and DSC methods,and by the capacity to make stand-alone films. From the measurements of the intrinsic viscosity in acetonitrile, theMn ranges from 16000 to 18400 (12 to 16 units). The dinuclear model complex [Pd2(dmb)2(PPh3)2](ClO4)2 (4) isprepared and investigated as well. The molecular dynamic of the title polymers in acetonitrile solution is investigatedby means of 13C spin-lattice relaxation time (T1) and nuclear Overhauser enhancement methods (NOE). Thenumber of units determined by T1/NOE methods is 3 to 4 times less than that found from the measurements ofintrinsic viscosity, and is due to flexibility in the polymer backbone, even for bridging ligands containing only one(dmb) or two C-C single bonds (dpa). During the course of this study, the starting material Pd2(dmb)2Cl2 wasreinvestigated after evidence for oligomers in the MALDI-TOF spectrum was noticed. In solution, this d9-d9 speciesis a binuclear complex (T1/NOE). This result suggests that the structure of the title polymers in solution and in thesolid state may not be the same either. Finally, these polymers are strongly luminescent in PrCN glasses at 77 K,and the photophysical data (emission lifetimes, 1.50 < 
e < 2.75 ns; quantum yields, 0.026 < 
e < 0.17) arepresented. X-ray data for [Pd2(dppe)2(dmb)2](PF6)4: monoclinic, space group C2/c, a = 24.3735 Å, b = 21.8576(13) Å, c = 18.0034(9) Å, b = 119.775(1)
deg.gif">, V = 8325.0(8) Å3, Z = 4.
da.gif" BORDER=0 >max(d-d*) < 480 nm), by ATG, XRD, and DSC methods,and by the capacity to make stand-alone films. From the measurements of the intrinsic viscosity in acetonitrile, theMn ranges from 16000 to 18400 (12 to 16 units). The dinuclear model complex [Pd2(dmb)2(PPh3)2](ClO4)2 (4) isprepared and investigated as well. The molecular dynamic of the title polymers in acetonitrile solution is investigatedby means of 13C spin-lattice relaxation time (T1) and nuclear Overhauser enhancement methods (NOE). Thenumber of units determined by T1/NOE methods is 3 to 4 times less than that found from the measurements ofintrinsic viscosity, and is due to flexibility in the polymer backbone, even for bridging ligands containing only one(dmb) or two C-C single bonds (dpa). During the course of this study, the starting material Pd2(dmb)2Cl2 wasreinvestigated after evidence for oligomers in the MALDI-TOF spectrum was noticed. In solution, this d9-d9 speciesis a binuclear complex (T1/NOE). This result suggests that the structure of the title polymers in solution and in thesolid state may not be the same either. Finally, these polymers are strongly luminescent in PrCN glasses at 77 K,and the photophysical data (emission lifetimes, 1.50 < e < 2.75 ns; quantum yields, 0.026 < e < 0.17) arepresented. X-ray data for [Pd2(dppe)2(dmb)2](PF6)4: monoclinic, space group C2/c, a = 24.3735 Å, b = 21.8576(13) Å, c = 18.0034(9) Å, b = 119.775(1)deg.gif">, V = 8325.0(8) Å3, Z = 4.© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |