First hyperpolarizabilities of vinylogue organometallic sesquifulvalene chromophores: A DFT study

Abstract

The metal-to-ligand charge-transfer contributes to the first hyperpolarizability and, as a result, the rational substitution of coordinated metal could modulate the first hyperpolarizability of the organometallic chromophores. The study would be helpful to understand optical nonlinearities in organometallic complexes.

First Hyperpolarizability Evolutions of Some Extended Sesquifulvalene Compounds

“…Actually, the smaller basis set, Lanl2MB, with the combination of B3LYP functional in our previous work 8 can also adequately well predict the first hyperpolarizability magnitudes of this class of compounds. On the other hand, according to our previous calculations for some present molecules, 7 the LanL2DZ basis set is adequately accurate since the calculated results agree well with the experimental values. Furthermore, molecular sizes of sandwich complexes with transition metal are so large that the application of the larger basis set is impractical.…”

“…We employ a specific uniform external electric field, F i ＝0.0010 atomic units, which has previously been illustrated to be appropriate for β iii and β ijj calculations. 7 Ultimately, the spatiallyoriented averaged magnitudes as µ, α, and β are deduced …”

“…As we know, the density functional theory (DFT) [12][13][14][15] is the most powerful computational tool to explore the structures and properties of organic transition metal compounds due to its affordable computational cost and high computational precision. Our previous computational investigations 7,8 suggest that the DFT method can be reasonably used to predict β of sesquifulvalene-type transition metal complexes in comparison to the calculated results and the experimental values. The coordination of sesquifulvalene with monoand bi-metallic fragments can effectively modulate β and the introduction of vinyl, ethynyl, phenyl spacers can remarkably enhance β.…”

“…[4][5][6] With the purposes of exploring NLO microscopic origin and predicting the first hyperpolarizability magnitude, we have theoretically carried out molecular orbital calculations. 7,8 A conjugated linking spacer such as olefins, thiophenes, vinylenethienylenes between the electron donor (the metallocenyl moiety) and the electron acceptor (the tropylium cation) usually can maximize the first hyperpolarizability. The typical examples are sesquifulvalene cyclopentadienyl-iron(II) complexes [CpFeC 5 H 4 -(E-CH＝ CH) n - 7 6 C H ; ＋ n ＝ 1 -3] and [CpFeC 5 H 4 (C 4 H 2 S) n - 7 6 C H ; ＋ n ＝ 1 -2].…”

Spectroscopic and theoretical optical properties of indoleninyl‐substituted dibenzotetraaza[14]annulenes

“…[ 31 ] The hyper‐polarizability tensor components of the organic and organometallic materials are extensively derived by means of the B3LYP function. [ 32,33 ] It is known that the subject functional generates the logical experimental trends. [ 34,35 ] The calculated averaged orientation (isotropic) dipole polarizability < α > and the β tot (total first static hyper‐polarizability) are as follows: [ 36 ] …”