The Alkaline-earthides based parallel-stacked dimer and trimer of Janus face C6H6F6 showing extremely large nonlinear optical responses

Superalkali-alkaline earthide ion pairs of δ+(AM-HMHC)-AM′δ− (AM = Li, Na and K; AM′ = Be, Mg and Ca) possessing large NLO responses and excellent electronic stabilities and alkalide characteristics: a DFT study

“…21 The b e 0 values of alkaline-earthides of Na(C 6 H 6 F 6 ) 2 Be, Na(C 6 H 6 F 6 ) 2 Mg, Li(C 6 H 6 F 6 ) 3 Mg, and Li(C 6 H 6 F 6 ) 3 Ca are 1.21 Â 10 4 , 9.00 Â 10 3 , 3.31 Â 10 4 , and 3.43 Â 10 4 a.u., respectively. 25 Among these b e 0 values, our superalkali-alkaline earthide ion pairs of both the chair and boat forms of d+ (AM-HMHC)-AM 0dÀ (M = Li, Na, and K; AM 0 = Be, Mg, and Ca) have excellent NLO responses.…”

“…To date, reported alkalides mainly refer to the following four categories: alkalide, 3,[6][7][8][9][10][11][12] coinage metalide, 13,14 superalkalide, [15][16][17][18] and alkalineearthide. [19][20][21][22][23][24][25] For example, Ayub et al obtained the alkalide of M@[15-crown-5] 11 and M-(C 6 F 6 H 6 ) 2 -M; 12 superalkalide of Li 3 O@[12-crown-4]M; 15 and alkaline-earthide of M + (calix [4] pyrrole)M 0À , M + (NH 3 ) 6 M 0À , and M + (3 6 Adz)M 0À (M = Li, Na, and K; M 0 = Be, Mg, and Ca). [19][20][21] However, doping atoms, particularly alkali metal atoms, are very active, and subsequently, the chemical environment for the achievement of alkalide species is quite rigorous.…”

Poled polymers and their nonlinear optics

“…4(a)). 27,28 It can be considered that D-13N is composed of two low generation dendrimers located in the x and anti-x direction. The structure is approximately symmetrical and conforms to the ideal molecular conformation, which is beneficial for the poling orientation and the SNLO effect.…”

Enhanced nonlinear optical response of alkalides based on stacked Janus all-cis-1,2,3,4,5,6-hexafluorocyclohexane

“…Moreover, the alkaline earthide nature of M–C 6 H 6 F 6 –M′, has also been demonstrated by Ayub and coworkers by doping with alkali metals at fluorine face and alkaline earth metal atoms on hydrogen face [ 29 ]. A step further, the NLO properties of transition metal doped C 6 H 6 F 6 complexant have also been studied by Zhang et al [ 32 ], and Ayub et al, [ 33 ]. Literature reveals that the stacked orientations of C 6 H 6 F 6 , such as dimer; (C 6 H 6 F 6 ) 2 , and trimer; (C 6 H 6 F 6 ) 3 , have been reported by Pratik et al , [ 4 ] found that parallel-stacked C 6 H 6 F 6 are most stable because of the strong hydrogen bonding (C–H⋯F).…”

“…Literature reveals that the stacked orientations of C 6 H 6 F 6 , such as dimer; (C 6 H 6 F 6 ) 2 , and trimer; (C 6 H 6 F 6 ) 3 , have been reported by Pratik et al , [ 4 ] found that parallel-stacked C 6 H 6 F 6 are most stable because of the strong hydrogen bonding (C–H⋯F). The alkaline earthide based dimer and trimer of C 6 H 6 F 6 (M−C 6 H 6 F 6 -M′, where M is alkali metal and M' is alkaline earth metal) exhibited largest hyperpolarizability (1.5 × 10 7 au), which was 20 fold larger than M-C 6 H 6 F 6 (7 × 10 5 au), This is, because, the charge density is increased significantly upon adding stacked units [ 32 ]. Therefore, the stacked system of C 6 H 6 F 6 are the best candidates to design alkalides type nonlinear optical material.…”