Two temperature-induced 1D Cu^II chain enantiomeric pairs showing different magnetic properties and nonlinear optical responses

Abstract

At different reaction temperatures, using Cu(NO3)2•3H2O to react with enantiomerically pure N-donor ligands (LS and LR), respectively, two pairs of chiral one-dimensional (1D) CuII chain enantiomers formulated as [Cu(μ2-NO3)(NO3)(LS)]n/[Cu(μ2-NO3)2(NO3)(LR)]n (S-1-Cu/R-1-Cu,...

Two pairs of chiral YbIII enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses

“…In order to confirm this fact, DFT calculations on the dipole moments of D-1 and D-2 were performed using the Gaussian 09 package, and the results unveil that the dipole moment ( μ total = 7.14 D) of D-1 is much larger than that of D-2 ( μ total = 2.73 D) (Table S7†). Moreover, as shown in Table 1, the SHG intensities of D-1/L-1 are much larger than those of most reported SHG-active complexes, such as 1D chiral Cu( ii ) enantiomers with L R /L S ligands, 81 [Dy(dma) 5 ][W(CN) 8 ], 110 chiral R / S -FeNb enantiomers, 111 chiral YbZn 2 enantiomers, 112 chiral L/D-ZnBr 3 enantiomers, 113 (CASD) 2 MnBr 4 , 114 [(DPA)(18-crown-6)]ClO 4 , 115 chiral 2D Ag( i ) enantiomers, 80 a chiral Cu( i ) complex, 116 N*[MnCr], 117 C 2 H 10 N 2 ·Mg(H 2 PO 3 ) 2 (C 2 O 4 ), 118 [C(NH 2 ) 3 ] 2 Zn(CO 3 ) 2 , 119 ionic 1D chiral Cu( ii ) enantiomers with L R /L S ligands, 72 [Cd(en)-(1,3-dap)][AlB 5 O 10 ], 120 (morpholinium) 2 Cd 2 Cl 6 , 121 (C 4 H 10 NO)PbBr 3 , 122 [C(NH 2 ) 3 ] 3 AsO 4 ·2H 2 O, 123 and (Hdabco + )(CF 3 COO − ), 124 but slightly smaller than those of some complexes, such as a YbSe complex 125 and [(CH 3 ) 3 NCH 2 CHCH 2 ]FeCl 4 . 126 More remarkably, the SHG intensities of D-1/L-1 are even more than twice those of inorganic SHG-active materials, for example KTOH 127 and CKBFI.…”

“…6d), which are In order to confirm this fact, DFT calculations on the dipole moments of D-1 and D-2 were performed using the Gaussian 09 package, and the results unveil that the dipole moment (μ total = 7.14 D) of D-1 is much larger than that of D-2 (μ total = 2.73 D) (Table S7 †). Moreover, as shown in Table 1, the SHG intensities of D-1/L-1 are much larger than those of most reported SHG-active complexes, such as 1D chiral Cu(II) enantiomers with L R /L S ligands, 81 123 and (Hdabco + )(CF 3 COO − ), 124 but slightly smaller than those of some complexes, such as a YbSe complex 125 and [(CH 3 ) 3 NCH 2 CHCH 2 ]FeCl 4 . 126 More remarkably, the SHG intensities of D-1/L-1 are even more than twice those of inorganic SHG-active materials, for example KTOH 127 and CKBFI.…”

“…We are interested in the synthesis of NCS complexes based on various chiral N-donor ligands due to their unique chirality-relevant properties, such as ferroelectricity, 9,73–77 CPL, 10,78 and SHG response. 79–81 Very recently we reported two eight- and nine-coordinated mononuclear Yb III enantiomeric pairs with the same β-diketonate but different chiral N-donor ligands, and the NIR photoluminescence (NIR-PL), NIR-CPL and SHG performances of eight-coordinated Yb III enantiomers are much better than those of the nine-coordinated ones. 78 This result encouraged us to explore Yb III complexes with NCS structures based on identical chiral N-donors but different β-diketonate ligands with distinct structural features to further probe their NIR-PL, NIR-CPL and NLO properties.…”

Two chiral lanthanide PrIII and HoIII complexes: NIR luminescence and nonlinear optical properties

“…We are interested in the construction of chiral complexes with enantiopure N-containing ligands, showing luminescence, magnetic, ferroelectric and NLO properties. [63][64][65][66][67][68][69][70][71][72][73] In terms of NLO-active complexes, our research results demonstrate that organic ligands with large π-conjugated systems and symmetric molecular structures are beneficial for the corresponding complexes to exhibit THG responses, [63][64][65] while organic ligands with asymmetric D (donor)-π-A (acceptor) molecular structures are conducive to the occurrence of SHG responses in the corresponding complexes. 64,65 Based on these findings and aforementioned research backgrounds of Ln III complexes with NIR-emissions and NLO responses, we intend to develop Pr III and Ho III complexes not only displaying NIR-emissions but also possessing SHG and THG responses simultaneously.…”

A pair of ionic 1D Cu(ii) chain enantiomers simultaneously displaying large second- and third-harmonic generation responses

“…25 However, the reported CPs with both SHG and THG responses are very scarce. [27][28][29][30] In particular, there has been no example of chiral CPs presenting simultaneously large THG and SHG responses.…”