Prediction of remarkably large second-order nonlinear optical properties of organoimido-substituted hexamolybdates.
The dipole polarizabilities, dipole moments, density of states, and second-order nonlinear optical (NLO) properties of organoimido derivatives of hexamolybdates have been investigated by using time-dependent density functional response theory. This class of organic-inorganic hybrid compounds possesses remarkably large and eye-catching molecular second-order NLO response, especially [Mo(6)O(17)(NC(16)H(12)NO(2))(FeNC(10)H(9))](2-) (7) and [Mo(6)O(17)(NC(16)H(12)NO(2))(NC(6)H(2)(NH(2))(3))](2-) (6) with static second-order polarizability (beta(vec)) computed to be 15766.27 x 10(-30) esu and 6299.59 x 10(-30) esu, respectively. Thus, these systems have the possibility to be excellent second-order nonlinear optical materials. Analysis of the major contributions to the beta(vec) value suggests that the charge transfer (CT) from polyanion to organic segment (D-A) along the z-axis plays the key role in NLO response; the polyanion acts as a donor (D) whereas organoimido acts as an acceptor (A) in all the studied systems. The computed beta(vec) values increase by incorporation of an electron acceptor (-NO(2)) at the end of the phenyl ring of the organoimido segment. Furthermore, substitution of amino (-NH(2)) or ferrocenyl (-FeC(10)H(9)) at the outer side of polyanion and an electron acceptor (-NO(2)) at the end of the phenyl ring in organoimido segment simultaneously is more important to enhance the optical nonlinearity. Orbital analysis shows that the degree of CT between the polyanion and organoimido segments was increased when ferrocenyl donor was introduced. The present investigation provides important insight into the remarkably large NLO properties of organoimido-substituted hexamolybdates.
Janjua
Muhammad Ramzan Saeed Ashraf
MR
Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China.
Liu
Chun-Guan
CG
Guan
Wei
W
Zhuang
Jia
J
Muhammad
Shabbir
S
Yan
Li-Kai
LK
Su
Zhong-Min
ZM
D007097:Imines / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D055620:Optical Phenomena; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013329:Structure-Activity Relationship
D007097:Imines; D009942:Organometallic Compounds; C044659:molybdate; D008982:Molybdenum