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

Abstract

Employing enantiomerically pure mono-bidentate N-donors (LR/LS) as chiral bridging ligands to react with Cu(ClO4)2(H2O)6 in CH3CN-DMF mixed solvent, respectively, a pair of ionic one-dimensional (1D) Cu(II) chain enantiomers formulated as...

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

“…We believe that D-1/L-1 show such outstanding SHG performances and exhibit much larger SHG responses than D-2/L-2 mainly thanks to the btfa − ligand containing a –CF 3 group with large polarity, 109 resulting in a large dipole moment in D-1/L-1 which is beneficial for the observation of larger SHG responses in D-1/L-1 . 71,72…”

“…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.…”

“…In particular, it is well recognized that the SHG response is a polarity-dependent process and using organic ligands with different polarities to assemble the NLO-active complexes should give them different molecular dipole moments, which can realize the modulation of their SHG performances. 71,72…”

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. 63–73 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, 63–65 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…”

1D Cu(i)-based chiral organic–inorganic hybrid material with second harmonic generation and circular polarized luminescence

“…41 Nevertheless, research on the NLO properties of copper-based organic–inorganic Hybrids is relatively limited. 36,42,43 In addition, Cu( i ) complexes possess abundant electron transitions, which usually endow them with excellent photophysical properties.…”