Crystal engineering, the ability to predict and control the packing of molecular building units in the solid state, has attracted much attention over the past three decades owing to its potential exploitation for the synthesis of technologically important materials. We present here the development of crystal-engineering strategies toward the synthesis of noncentrosymmetric infinite coordination networks for use as second-order nonlinear optical (NLO) materials. Work performed mainly in our laboratory has demonstrated that noncentrosymmetric solids based on infinite networks can be rationally synthesized by combining unsymmetrical bridging ligands and metal centers with well-defined coordination geometries. Specifically, coordination networks based on 3D diamondoid and 2D grid structures can be successfully engineered with a high degree of probability and predictability to crystallize in noncentrosymmetric space groups. We have also included noncentrosymmetric solids based on 1D chains and related helical structures for comparison.

Crystal engineering of NLO materials based on metal-organic coordination networks

We have measured the second and third order hyperpolarizabilities of the three nitroaniline isomers and of two related molecules. For some isomers the intramolecular charge transfer is found to cause a very large enhancement of the second order polarizabilities. We present a theory relating this contribution to the first excited state of energy, oscillator strength, and dipole moment of the molecules. Experimental results are accounted for with an excellent accuracy.

Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment

The hybrid two-dimensional (2D) halide perovskites have recently drawn significant interest because they can serve as excellent photoabsorbers in perovskite solar cells. Here we present the large scale synthesis, crystal structure, and optical characterization of the 2D (CH3(CH2)3NH3)2(CH3NH3)n−1PbnI3n+1 (n = 1, 2, 3, 4, ∞) perovskites, a family of layered compounds with tunable semiconductor characteristics. These materials consist of well-defined inorganic perovskite layers intercalated with bulky butylammonium cations that act as spacers between these fragments, adopting the crystal structure of the Ruddlesden–Popper type. We find that the perovskite thickness (n) can be synthetically controlled by adjusting the ratio between the spacer cation and the small organic cation, thus allowing the isolation of compounds in pure form and large scale. The orthorhombic crystal structures of (CH3(CH2)3NH3)2(CH3NH3)Pb2I7 (n = 2, Cc2m; a = 8.9470(4), b = 39.347(2) A, c = 8.8589(6)), (CH3(CH2)3NH3)2(CH3NH3)2Pb3I10 (...

http://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.6b00847

Ruddlesden-Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors

Sources and systems for far-infrared or terahertz (1 THz = 10(12) Hz) radiation have received extensive attention in recent years, with applications in sensing, imaging and spectroscopy. Terahertz radiation bridges the gap between the microwave and optical regimes, and offers significant scientific and technological potential in many fields. However, waveguiding in this intermediate spectral region still remains a challenge. Neither conventional metal waveguides for microwave radiation, nor dielectric fibres for visible and near-infrared radiation can be used to guide terahertz waves over a long distance, owing to the high loss from the finite conductivity of metals or the high absorption coefficient of dielectric materials in this spectral range. Furthermore, the extensive use of broadband pulses in the terahertz regime imposes an additional constraint of low dispersion, which is necessary for compatibility with spectroscopic applications. Here we show how a simple waveguide, namely a bare metal wire, can be used to transport terahertz pulses with virtually no dispersion, low attenuation, and with remarkable structural simplicity. As an example of this new waveguiding structure, we demonstrate an endoscope for terahertz pulses.

Metal wires for terahertz wave guiding

Nonlinear optical properties are a sensitive probe of the electronic and solid-state structure of organic compounds and as a consequence find various applications in many areas of optoelectronics including optical communications, laser scanning and control functions, and integrated optics technology. Because of their strongly delocalized π electronic systems, polymeric and non-polymeric aromatic compounds show highly nonlinear optical effects. Nowadays, polymer chemists are able to tailor specific materials properties for various applications. Some organic substances with π electronic systems exhibit the largest known nonlinear coefficients, often considerably larger than those of the more conventional inorganic dielectrics and semiconductors, and thus show promise for thin-film fabrication, allowing the enormous function and cost advantages of integrated electronic circuitry. The electronic origins of nonlinear optical effects in organic π electronic systems are reviewed, with special emphasis being given to second-order nonlinear optical effects. Methods for measuring nonlinear optical responses are outlined, and the critical relationships of the propagation characteristics of light to observed nonlinear optical effects and to solid-state structure are discussed. Finally, the synthesis and characterization of organic crystals and polymer films with large second-order optical nonlinearities are summarized.

Organic Polymeric and Non-Polymeric Materials with Large Optical Nonlinearities

An experimental technique using powders is described which permits the rapid classification of materials according to(a) magnitude of nonlinear optical coefficients relative to a crystalline quartz standard and(b) existence or absence of phase matching direction(s) for second‐harmonic generation.Results are presented for a large number of inorganic and organic substances including single‐crystal data on phase‐matched second‐harmonic generation in HIO3, KNbO3, PbTiO3, LiClO4·3H2O, and CO(NH2)2. Iodic acid (HIO3) has a nonlinear coefficient d14∼1.5×d31 LiNbO3. Since it is readily grown from water solution and does not exhibit optical damage effects, this material should be useful for nonlinear device applications.

T. T. Perry

Papers

A Powder Technique for the Evaluation of Nonlinear Optical Materials

A powder technique for the evaluation of nonlinear optical materials