Novel Pb and Zn Coordination Polymers: Synthesis, Molecular Structures, and Third-Order Nonlinear Optical Properties
- 17 January 2003
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 42 (4), 1306-1315
- https://doi.org/10.1021/ic0259282
Abstract
Three novel coordination polymers [Pb(bbbm)2(NO3)2]n (bbbm = 1,1‘-(1,4-butanediyl)bis-1H-benzimidazole) 1, [Zn(bbbt)(NCS)2]n (bbbt = 1,1‘-(1,4-butanediyl)bis-1H-benzotriazole) 2, and [Zn(pbbt)(NCS)2]n (pbbt = 1,1‘-(1,3-propylene)bis-1H-benzotriazole) 3 were synthesized and structurally characterized. Polymer 1 exhibits a two-dimensional rhombohedral grid network structure, the dimensions of the grid are 14.274 × 14.274 Å, and the diagonal-to-diagonal distances are 24.809 × 14.125 Å. Polymer 2 possesses a concavo-convex chain structure different from those of the known one-dimensional polymers, which are linear chain, zigzag chain, helical chain, double-stranded chain, and ladder chain. Polymer 3 exhibits a one-dimensional zigzag chain structure, and these chains were packed as an ...ABAB... layered structure. The third-order nonlinear optical (NLO) properties of polymers 1, 2, and 3 were determined with a 7-ns pulsed laser at 532 nm. 1 shows strong third-order NLO absorptive and refractive properties, and its α2 and n2 values were calculated to be 5.8 × 10-9 m W-1 and 4.67 × 10-18 m2 W-1 in a 3.4 × 10-4 mol dm-3 DMF solution, respectively. Both 2 and 3 exhibit weaker NLO absorption and strong refractive properties, and their n2 values are 4.53 × 10-18 m2 W-1 for 2 in a 5.2 × 10-4 mol dm-3 DMF solution and 3.02 × 10-18 m2 W-1 for 3 in a 4.35 × 10-4 mol dm-3 DMF solution. The χ(3) values of 1, 2, and 3 were calculated to be 1.67 × 10-11, 1.62 × 10-11, and 1.08 × 10-11 esu, respectively, and the values are larger than those of the reported coordination polymers. We deduce that the valence shell structures of metal ions may have some influence on the strength of NLO properties, and discuss the relationships between the crystal structures of coordination polymers and the observed NLO properties.Keywords
This publication has 73 references indexed in Scilit:
- A Novel Octupolar Metal−Organic NLO Material Based on a Chiral 2D Coordination NetworkJournal of the American Chemical Society, 1999
- A New Type of Metal-Organic Large-Pore ZeotypeAngewandte Chemie-International Edition, 1999
- Self-assembly of novel co-ordination polymers containing polycatenated molecular ladders and intertwined two-dimensional tilingsJ. Chem. Soc., Dalton Trans., 1999
- Synthesis, crystal structure and large third-order nonlinear optical properties of two novel nest-shaped clusters [MOS3Cu3(SCN)(Py)5] (M=Mo, W)Physical Chemistry Chemical Physics, 1999
- Polycatenated copper(I) molecular ladders: a new structural motif in inorganic coordination polymersChemical Communications, 1997
- Molecular structures, macroscopic nonlinear optical effects, and photonic devicesContemporary Physics, 1994
- Synthesis, structure, and vibrational spectrum of poly-μ-pyrazine(pyrazine)(trifluoromethanesulfonato-O)copper(I)Canadian Journal of Chemistry, 1989
- Third-order non-linear optical properties of oriented films of poly(p-phenylene vinylene) investigated by femtosecond degenerate four wave mixingPolymer, 1988
- Conductive and optically non-linear polymeric langmuir-blodgett films of poly(3-dodecylthiophene)Synthetic Metals, 1988
- Time and wavelength resolved nonlinear optical spectroscopy of a polydiacetylene in the solid state using picosecond dye laser pulsesApplied Physics Letters, 1985