The 1:1 reaction between the d
9-d
9 Pd
2(dmb)
2Cl
2 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 LiClO
4leads to the {[Pd
2(dmb)
2(diphos)](ClO
4)
2}
n polymers. These new materials are characterized by NMR (
1H,
13C,
31P), IR, Raman, and UV-vis spectroscopies (466 <
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, the
Mn ranges from 16000 to 18400 (12 to 16 units). The dinuclear model complex [Pd
2(dmb)
2(PPh
3)
2](ClO
4)
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 Pd
2(dmb)
2Cl
2 wasreinvestigated after evidence for oligomers in the MALDI-TOF spectrum was noticed. In solution, this d
9-d
9 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 [Pd
2(dppe)
2(dmb)
2](PF
6)
4: monoclinic, space group
C2/
c,
a = 24.3735 Å,
b = 21.8576(13) Å,
c = 18.0034(9) Å,
b = 119.775(1)
,
V = 8325.0(8) Å
3,
Z = 4.