Novel vanadium‐containing polymers prepared from bis(arene)vanadium and acrylonitrile: third‐order non‐linear optical properties

Abstract

Treatment of (arene)2 V with acrylonitrile in the presence of a catalytic amount of tetracyanoethylene affords vanadium‐containing polyacrylonitrile. Thermolysis of the latter at 350 °C gives a naphthyridine‐type polymer containing 16% vanadium. Z‐scan measurements at 1064 nm for a solution of this thermolysed material in concentrated H2SO4 (c, 1 g l−1) gave a value of −1.8 × 10−13 cm2 W−1 (corresponding to Reχ(3) = −0.9 × 10−11 esu) for the electronic contribution to n2. The Z‐scan did not show any two‐photon absorption for beam intensities up to 0.3 GW cm−2. The vanadium‐containing polyacrylonitrile readily forms transparent films on casting from acetonitrile solution. © 2002 Society of Chemical Industry

Organometallic self-organized nanomaterials for nonlinear optics

“…(2) The results obtained for acrylonitrile and crotononitrile confirm the mechanism we suggested previously of aromatic ring cyanoethylation with further polymerization. 4 Thus, the signal at 55.7 ppm in the solid-state 13 C NMR spectrum of CrPAN, which is absent in the spectra of both the pure complex and polyacrylonitrile, can be assigned to the acrylonitrile CH 2 groups covalently bonded to the arene ligand.…”

“…The properties of thermolysed bis(arene)metal-containing polyacrylonitrile (MPAN) are consistent with the formation of conjugated ladder-type polynaphthyridine structures. 3,4 Thus, MPAN turns out to be a promising polymer-precursor for the preparation of non-linear optical structures: the value of electronic n 2 determined by the DFWM and Z-scan technique at 1064 nm with a 6 ns pulse duration for a solution in conc. H 2 SO 4 (1 gl -1 ) of the Cr-and V-containing polymers pyrolyzed at 350°C was found to be 0.8 x 10 -13 cm 2 W -1 and 2.2 x 10 -13 cm 2 W -1 , respectively.…”

“…[1][2][3][4][5] The resulting star-shaped molecules consist of a central (arene) 2 M species with polyacrylonitrile arms covalently bonded to the arene ligands. The properties of thermolysed bis(arene)metal-containing polyacrylonitrile (MPAN) are consistent with the formation of conjugated ladder-type polynaphthyridine structures.…”

Chromium-containing organometallic nanomaterials for non-linear optics

“…Previously, we have reported the synthesis of (arene) 2 Mcontaining polyacrylonitrile (M = Cr,V) prepared by the polycyanoethylation reaction between bis-arene complexes and acrylonitrile. [1][2][3][4][5] The resulting star-shaped molecules consist of a central (arene) 2 M species with polyacrylonitrile (PAN) arms covalently bonded to the arene ligands. The properties of thermolysed bis(arene)metal-containing polyacrylonitrile (MPAN) are consistent with the formation of conjugated ladder-type polynaphthyridine structures.…”

“…The properties of thermolysed bis(arene)metal-containing polyacrylonitrile (MPAN) are consistent with the formation of conjugated ladder-type polynaphthyridine structures. 3,4 Thus, MPAN turns out to be a promising polymeric nanocomposite precursor for the preparation of non-linear optical structures: the value of electronic n 2 determined by the DFWM and Z-scan technique at 1064 nm with a 6 ns pulse duration for a solution in concentrated H 2 SO 4 (1 g l À1 ) of the Cr-and V-containing polymers pyrolyzed at 350 1C was found to be 0.8 Â 10 À13 cm 2 W À1 and 2.2 Â 10 À13 cm 2 W À1 , respectively.…”