Multidecker Sandwich Complexes V(n)Ben(n+1) (n=1, 2, 3) as Stronger Electron Donor Relative to Ferrocene for Designing High-Performance Organometallic Second-Order NLO Chromophores: Evident Layer Effect on the First Hyperpolarizability and Two-Dimensional NLO Character

摘要

During the past 3 decades, significant progress has been made in multidecker sandwich complexes. Replacing rrietallocene in the metallocene-based second-order nonlinear optical to with multidecker sandwich complexes will create a variety of second-order NLO organometallic complexes. To explore the possibility of improving NLO properties of organometallic complexes by using multidecker sandwich complexes, we theoretically design five second-order NLO moleculars V(n)Bz(n+1)-(C2H2)(3)-NO2 (n = 1, 2, 3) with widely investigated V(n)Bz(n+1) (n = 1, 2, 3) by changing the layer number n or position of conjugation g A system in the Di r A structure. The NLO properties of these five complexes are investigated in detail. By comparison with the fio of ferrocenyl derivative Fe(eta(5)-C5H5)(2)-(C2H2)(3)-NO2, the larger NLO response (beta(0), 10215-36917 au) is found in V(n)Bz(n+1)-(C2H2)(3)-NO2 (n = 1, 2, 3). The dependence of the first hyperpolarizabilities beta(0) on the layer number h and the position of conjugation pi-A system is discussed in-ithe article. The evident layer effect on the first hyperpolarizabilities beta(0) is shown. And, the enlargement of the first hyperpolatiability beta(0) by the layer number n can be rationalized by considering the enhancement of parallel-x-MLCT (fibril more than one metal center to acceptor, -NO2), perpendicular-x-MLCT (from multiple metal centers to multiple C6H6 ligafids) transition and two-dimensional NLO character with the two charge transfer axes. By comparison with fettocene or V(1)Bz(2), the multidecker sandwich complexes V(n)Bz(n+1) (n = 2, 3) can be considered as stronger donor group for designing NLO moletulars. We hope, this groundbreaking work may evoke one's attention to design new, highly efficient second-order NLO molecular materials with excellent building blocks: Multidecker sandwich complexes.