Tuning the dipolar second-order nonlinear optical properties of 5-π-delocalized-donor-1,3-di(2-pyridyl)benzenes, related cyclometallated platinum(ii) complexes and methylated salts

Abstract

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Novel cyclometallated 5-π-delocalized donor-1,3-di(2-pyridyl)benzene platinum(ii) complexes with good second-order nonlinear optical properties

“…28 The good second-order nonlinear optical properties of various platinum(II) complexes with a cyclometallated 1,3-di(2-pyridyl)benzene, well-known for their emissive properties, 29 have also been evidenced by the Electric-Field Induced Second Harmonic generation (EFISH) technique. [30][31][32] In particular, the cyclometallated Pt(II) chloro Please do not adjust margins Please do not adjust margins the ground state (µ = 10.7 D) and a good second-order NLO response (µβ EFISH = -880 x 10 -48 esu) mainly determined by a charge transfer transition from platinum to the cyclometallated ligand. 31 Similar values (µ = 9.4 D; µβ EFISH = -820 x 10 -48 esu) were obtained by substitution of the N,Ndiphenylamino group by a pyrene moiety.…”

“…[30][31][32] In particular, the cyclometallated Pt(II) chloro Please do not adjust margins Please do not adjust margins the ground state (µ = 10.7 D) and a good second-order NLO response (µβ EFISH = -880 x 10 -48 esu) mainly determined by a charge transfer transition from platinum to the cyclometallated ligand. 31 Similar values (µ = 9.4 D; µβ EFISH = -820 x 10 -48 esu) were obtained by substitution of the N,Ndiphenylamino group by a pyrene moiety.…”

“…In agreement with this observation, the LUMOs of complexes Pt3 and Pt5, characterized by large β EFISH values despite higher HOMO-LUMO gaps than Pt1, are much more delocalized than the others of the Pt2-P6 series, Figure 1. Also, in the case of trans-5-(p-(N,N-diphenylamino)styryl)-1,3-di(2-pyridyl)benzene, 31 the decrease of the quadratic hyperpolarizability upon substitution of the double bond 31 by a thiophene (Pt2) can be related to the less delocalized LUMO. Such a decrease in the case of the pyrene derivatives doesn't occur because the LUMOs are delocalized also on the pyrene fragment both with the double bond 31 or the thiophene (Pt3) bridge.…”

An investigation on the second-order nonlinear optical response of cationic bipyridine or phenanthroline iridium(iii) complexes bearing cyclometallated 2-phenylpyridines with a triphenylamine substituent

“…[3][4][5][6][7][8][9][10][11] Such metal complexes, thanks to multiple transition with large oscillator strength, low bandgap, high dipole moment, have also been used with success in the framework of 3 rd order NLO, notably in the framework of two-photon fluorescence imaging. [12][13][14][15][16][17] Remarkably, the second-order NLO response of substituted phenylpyridines (ppy) increases significantly upon cyclometallation, an effect that has led to cyclometallated Ru(II), 18 Ir(III) [19][20][21][22][23][24][25][26][27][28][29][30] and Pt(II) 29,[31][32][33][34][35][36][37] complexes characterised by valuable NLO properties, as measured by the Electric Field Induced Second Harmonic generation (EFISH) technique. [38][39][40] More specifically, cationic cyclometallated iridium(III) complexes with -delocalised ancillary ligands such as bipyridines 24,30 or phenanthrolines [19][20][21]…”

Synthesis, crystal structure and NLO study of two new versatile Ca (II) complexes

“…The excellent NLO frequency conversion materials are utilized in many optoelectronics devices . The different types of supramolecular organic and inorganic hybrids are very useful for good NLO response in the push–pull process . The placement of metal nodes in organic conjugated moieties could effectively influence the charge transfer process during the frequency conversion process.…”