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

Abstract

For platinum complexes bearing a cyclometallated 5-thiophene-1,3-di(2-pyridyl)benzene, βEFISH increases following the order of the LUMO stabilization.

An excursion in the second-order nonlinear optical properties of platinum complexes

“…Similarly a large µβ1.907EFISH has been observed for compounds 54 (µβ1.907EFISH = -820 × 10 -48 esu, where β1.907EFISH = -87 × 10 -30 esu and µ =9.4 × 10 -18 esu) [95], 55 (µβ1.907EFISH = -1260 × 10 -48 esu, where β1.907EFISH = -133 × 10 -30 esu and µ =9.5 × 10 -18 esu) [95], 56 (µβ1.907EFISH = -660 × 10 -48 esu, where β1.907EFISH = -69 × 10 -30 esu and µ = 9.5 × 10 -18 esu) [96], and 57 (µβ1.907EFISH = -1540 × 10 -48 esu, where β1.907EFISH = -115 × 10 -30 esu and µ = 13.4 × 10 -18 esu) [97], much higher than that found for 47 (Figure 12). Thus, substitution of the methyl in 47 by a polarizable π-delocalized vinyl fragment causes a great intensification of the NLO activity.…”

“…The quadratic hyperpolarizabilities of a series of Pt(II) compounds functionalized with various thiophene fragments on the dipyridylbenzene were also investigated by the EFISH method (Figure 14 [97]). 60) leads to a decrease of β1.907EFISH because of the diminution of the LUMO's delocalization.…”

“…With the pyrene complexes, there is no decrease of the quadratic hyperpolarizability on going from 54 (with the double bond) to 61 (with thiophene) since in both cases there is delocalization of the lowest unoccupied molecular orbitals on the pyrene moiety. Therefore, delocalization of the LUMO not only on the pyridines but also on the moiety in position 5 of the 1,3dipyridylbenzene ligand appears crucial to improve the NLO activity of the Pt(II) family [97].…”

Charge Transfer Parameters, Correlative Perturbation Potential with Non‐Linear Optical Properties of Bi‐Heterocyclic Dyes Having TCF Acceptor‐ DFT Approach

“…[24] By using DFT, frequency dependant NLO properties or static hyperpolarizabilities can be calculated. [25][26][27] The degree of ground-state polarization or the degree of charge separation in the ground state, depends mainly on the chemical structure (D-π-A or -conjugated system) and the environment around the molecule i. e. solvent polarity. [28] Hence, we set a purpose to investigate the various ground state -charge transfer (CT) and NLO properties in different solvents and gas phase and correlations between them.…”

“…Predicting these properties by the computational method is relatively easy and can guide,while designing and development of NLOphoric materials [24] . By using DFT, frequency dependant NLO properties or static hyperpolarizabilities can be calculated [25–27] . The degree of ground‐state polarization or the degree of charge separation in the ground state, depends mainly on the chemical structure (D‐π‐ A or ‐conjugated system) and the environment around the molecule i. e. solvent polarity [28] .…”