The 1:1 reaction between the
d9-
d9 P
d2(
dmb)
2Cl
2 complex (
dmb = 1,8-
diisocyano-
p-menthane) an
d the
diphosphineligan
ds (
diphos) bis(
diphenylphosphino)butane (
5,
dppb), bis(
diphenylphosphino)pentane (
6,
dpppen), bis(
diphenylphosphino)hexane (
7,
dpph), an
d bis(
diphenylphosphino)acetylene (
8,
dpa) in the presence of LiClO
4lea
ds to the {[P
d2(
dmb)
2(
diphos)](ClO
4)
2}
n polymers. These new materials are characterize
d by NMR (
1H,
13C,
31P), IR, Raman, an
d UV-vis spectroscopies (466 <
da.gif" BORDER=0 >
max(
d-
d*) < 480 nm), by ATG, XRD, an
d DSC metho
ds,an
d by the capacity to make stan
d-alone films. From the measurements of the intrinsic viscosity in acetonitrile, the
Mn ranges from 16000 to 18400 (12 to 16 units). The
dinuclear mo
del complex [P
d2(
dmb)
2(PPh
3)
2](ClO
4)
2 (
4) isprepare
d an
d investigate
d as well. The molecular
dynamic of the title polymers in acetonitrile solution is investigate
dby means of
13C spin-lattice relaxation time (
T1) an
d nuclear Overhauser enhancement metho
ds (NOE). Thenumber of units
determine
d by
T1/NOE metho
ds is 3 to 4 times less than that foun
d from the measurements ofintrinsic viscosity, an
d is
due to flexibility in the polymer backbone, even for bri
dging ligan
ds containing only one(
dmb) or two C-C single bon
ds (
dpa). During the course of this stu
dy, the starting material P
d2(
dmb)
2Cl
2 wasreinvestigate
d after evi
dence for oligomers in the MALDI-TOF spectrum was notice
d. In solution, this
d9-
d9 speciesis a binuclear complex (
T1/NOE). This result suggests that the structure of the title polymers in solution an
d in thesoli
d state may not be the same either. Finally, these polymers are strongly luminescent in PrCN glasses at 77 K,an
d the photophysical
data (emission lifetimes, 1.50 <
e < 2.75 ns; quantum yiel
ds, 0.026 <
e < 0.17) arepresente
d. X-ray
data for [P
d2(
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)
deg.gif">,
V = 8325.0(8) Å
3,
Z = 4.