Organometallic and conjugated organic polymers held together by strong electrostatic interactions to form luminescent hybrid materials

Inorg Chem. 2008 Dec 15;47(24):11720-33. doi: 10.1021/ic801461j.

Abstract

The organometallic polymers ([Ag(dmb)(2)]BF(4))(n) (dmb = 1,8-diisocyano-p-menthane) and ([Pt(2)(dppm)(2)(CNC(6)Me(4)NC)](BF(4))(2))(n) (dppm = (Ph(2)P)(2)CH(2), CNC(6)Me(4)NC = 1,4-diisocyano-tetramethylbenzene) were reacted with the conjugated organic polymers of the type (-Cz-C(6)H(4)-)(n) and (-Cz-)(n), where Cz is a 2,7-linked carbazole unit substituted by (CH(2))(3)SO(3)Na or (CH(2))(4)SO(3)Na pendant groups at the N- position, to form polycation/polyanion hybrid materials. These rather insoluble and amorphous (X-ray diffraction) materials were characterized by (1)H and (13)C NMR MAS (magic angle spinning), solid-state IR, and Raman spectroscopy as well as chemical analyses. The hybrids exhibit fluorescence and phosphorescence arising from the polycarbazole units where evidence for a heavy atom effect is provided (Na < Ag < Pt) from the relative enhanced phosphorescence intensity, as well as triplet-triplet energy transfers from the ([Ag(dmb)(2)](+))(n) to the polycarbazole and from the polycarbazole to the ([Pt(2)(dppm)(2)(CNC(6)Me(4)NC)](2+))(n) unit. Evidence for energy transfer in these polymeric materials is provided from time-resolved emission spectroscopy, where the emission band associated with the ([Ag(dmb)(2)](+))(n) is found to be quenched where both the relative intensity and emission lifetime exhibit a large decrease (microsecond to nanosecond time scale).