Jump to main content
Jump to site search

Issue 42, 2013
Previous Article Next Article

A new type of organic–inorganic hybrid NLO-phore with large off-diagonal first hyperpolarizability tensors: a two-dimensional approach

Author affiliations

Abstract

We report a novel type of organic–inorganic hybrid material with rare two-dimensional nonlinear optical (NLO) properties. The density functional theory (DFT) calculations combined with the finite-field (FF) method show that the designed molecules (6,9 organo-derivatives of B10H14) could carry the characteristic NLO properties of both organic and inorganic materials. Interestingly, due to their unique V-shaped structures, they have large off-diagonal first hyperpolarizability tensors or nonlinear anisotropy, which is an advantage in their practical applications over conventional donor–π-acceptor (D–π-A) NLO-phores. The systematic substitutions of terminal donor/acceptor groups as well as the extension of π-conjugation along the V-shape in these derivatives have been evaluated to guide a purpose-oriented synthesis of NLO material. All the systems in the present study have been categorized into Set-I and Set-II with D–π-A–π-D and A–π-D–π-A configurations, respectively. These designed derivatives show large amplitudes of βz values. For example, systems 3N (6,9-[(N[double bond, length as m-dash]C[double bond, length as m-dash]Ph–NO2)2]-B10H12) and 4N (6,9-[((N[double bond, length as m-dash]C[double bond, length as m-dash]Ph)2-NO2)2]-B10H12) have βz amplitudes as large as 34.16 and 276.91 × 103 a.u. which are 380 and 3000 times larger than those of a typical NLO molecule of urea, respectively. Remarkably, the substitution of nitrogen atoms with 6,9 hydrogen atoms in decaborane is shown to cause a lone pair back donation to vacant p orbitals of 6,9 boron atoms of the decaborane basket. This p orbital overlapping verticalizes the V-arms of the decaborane derivatives and boosts their nonlinear anisotropies due to their larger off-diagonal tensor components. The nonlinear anisotropy values are significantly larger, ranging from 1 (minimum in system 1) to 31.90 (maximum in system 3A) due to their unique V-shape. Comparison of their efficiencies with standard molecules demonstrates that our designed organic–inorganic hybrid molecules have significant potential as excellent candidates for NLO applications.

Graphical abstract: A new type of organic–inorganic hybrid NLO-phore with large off-diagonal first hyperpolarizability tensors: a two-dimensional approach

Back to tab navigation

Supplementary files

Publication details

The article was received on 22 May 2013, accepted on 06 Aug 2013 and first published on 07 Aug 2013


Article type: Paper
DOI: 10.1039/C3DT51331A
Dalton Trans., 2013,42, 15053-15062

  •   Request permissions

    A new type of organic–inorganic hybrid NLO-phore with large off-diagonal first hyperpolarizability tensors: a two-dimensional approach

    S. Muhammad, H. Xu, Z. Su, K. Fukuda, R. Kishi, Y. Shigeta and M. Nakano, Dalton Trans., 2013, 42, 15053
    DOI: 10.1039/C3DT51331A

Search articles by author

Spotlight

Advertisements