Configurationally locked, phenolic polyene organic crystal 2-{3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene}malononitrile: linear and nonlinear optical properties

Hunziker, Christoph; Kwon, SangJoo; Figi, Harry; Juvalta, Flurin; Kwon, O‐Pil; Jazbinšek, Mojca; Günter, Peter

doi:10.1364/josab.25.001678

Cited by 77 publications

(64 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This crystal field effect anisotropy can be explained via an analysis of the crystal packing of OH1 which shows that the molecules form a head-to-tail sequential chain due to the strong OH···N intermolecular hydrogen bonding, and the main molecular charge-transfer direction is closely aligned with the z-direction (∼ ± 22°projected onto the bc plane). 13 To further support the conjecture that this OH···N hydrogen bond is the primary cause of the crystal field effects, DFT calculations were carried out on a series of dimer, trimer, tetramer, and pentamer clusters of OH1 molecules, using the B3LYP functional and both 6-31++G**/6-311+ +G** basis sets. These calculations realized an enhancement of ∼5 D between the dipole moment of the largest cluster relative to that of the isolated molecule (see Figure 6(a)); these findings are in line with the results obtained from the solid-state experimental charge-density study.…”

Section: (B) Harmonic-oscillator Stabilization Energy (Hose)mentioning

confidence: 99%

Molecular Origins of the High-Performance Nonlinear Optical Susceptibility in a Phenolic Polyene Chromophore: Electron Density Distributions, Hydrogen Bonding, and ab Initio Calculations

et al. 2013

Self Cite

View full text Add to dashboard Cite

The molecular and supramolecular origins of the superior nonlinear optical (NLO) properties observed in the organic phenolic triene material, OH1 (2-(3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile), are presented. The molecular charge-transfer distribution is topographically mapped, demonstrating that a uniformly delocalized passive electronic medium facilitates the charge-transfer between the phenolic electron donor and the cyano electron acceptors which lie at opposite ends of the molecule. Its ability to act as a "push−pull" π-conjugated molecule is quantified, relative to similar materials, by supporting empirical calculations; these include bond-length alternation and harmonicoscillator stabilization energy (HOSE) tests. Such tests, together with frontier molecular orbital considerations, reveal that OH1 can exist readily in its aromatic (neutral) or quinoidal (chargeseparated) state, thereby overcoming the "nonlinearity-thermal stability trade-off". The HOSE calculation also reveals a correlation between the quinoidal resonance contribution to the overall structure of OH1 and the UV−vis absorption peak wavelength in the wider family of configurationally locked polyene framework materials. Solid-state tensorial coefficients of the molecular dipole, polarizability, and the first hyperpolarizability for OH1 are derived from the first-, second-, and third-order electronic moments of the experimental charge-density distribution. The overall solid-state molecular dipole moment is compared with those from gas-phase calculations, revealing that crystal field effects are very significant in OH1. The solid-state hyperpolarizability derived from this charge-density study affords good agreement with gas-phase calculations as well as optical measurements based on hyper-Rayleigh scattering (HRS) and electric-field-induced second harmonic (EFISH) generation. This lends support to the further use of charge-density studies to calculate solid-state hyperpolarizability coefficients in other organic NLO materials. Finally, this charge-density study is also employed to provide an advanced classification of hydrogen bonds in OH1, which requires more stringent criteria than those from conventional structure analysis. As a result, only the strongest OH···NC interaction is so classified as a true hydrogen bond. Indeed, it is this electrostatic interaction that influences the molecular charge transfer: the other four, weaker, nonbonded contacts nonetheless affect the crystal packing. Overall, the establishment of these structure−property relationships lays a blueprint for designing further, more NLO efficient, materials in this industrially leading organic family of compounds. ■ INTRODUCTIONOrganic nonlinear optical (NLO) materials have received considerable attention in recent years due to numerous potential photonic applications; for example, optical switches, frequency converters, electro-optic modulators, as well as terahertz (THz) and spectroscopy applications. 1−4 Conjugated organic molecules containing ele...

show abstract

Section: (B) Harmonic-oscillator Stabilization Energy (Hose)mentioning

confidence: 99%

Molecular Origins of the High-Performance Nonlinear Optical Susceptibility in a Phenolic Polyene Chromophore: Electron Density Distributions, Hydrogen Bonding, and ab Initio Calculations

et al. 2013

Self Cite

View full text Add to dashboard Cite

show abstract

“…Compared with poled polymers, organic nonlinear optical crystals exhibit superior long-term temporal stability of the polar order of chromophores, higher chromophore density and superior photochemical stability 10 . However, in crystals efficient acentric packing of highly polar molecules is difficult to obtain and cannot be predicted solely based on the molecular structure yet 8 .…”

Section: Nonlinear Optics In Lifementioning

confidence: 99%

“…Crystals of named compounds were grown by slow evaporation technique at a fixed temperature, this technique is widely used by several groups of scientist all over the world [7][8][9][10][11][12][13][14]20,22,[25][26][27][28][29] . For the synthesis, an ethanol solution of 4-nitrophenol was added to an ethanol solution of each N-base (4-aminopyridine; 3,4-diaminopyridine; 2-amino-6-methylpyridine; 2,6-diaminopyridine; 2-aminopyridine).…”

Section: Fig 2 Structural Formulas Of Initial Reagentsmentioning

confidence: 99%

Organic noncentrosymmetric complexes of 4-nitrophenol for second harmonic generation

Pavlovetc

Draguta

Fokina

et al. 2015

Pacific Rim Laser Damage 2015: Optical Materials for High-Power Lasers

View full text Add to dashboard Cite

The paper reports synthesis and co-crystallization of 5 co-crystal of 4-nitrophenol (4N) with five different monoand diaminopyridines (4-aminopyridine (4AP); 3,4-diaminopyridine (34DAP); 2-amino-6-methylpyridine (26MAP); 2,6-diaminopyridine (26DAP); 2-aminopyridine (2AP)) resulted in five adducts with the molar ratio of components 2:1 in final compounds. X-ray analysis confirms the non-centrosymmetric packing of obtained compounds. Two compounds crystallize in the polar acentric P21 and three compounds crystallize in acentric orthorhombic Pna21 space groups. The comparative studies on the laser induced multiple and single shot damage thresholds of named crystals were carried out using radiation of 1064 nm from Nd:YAG laser with pulse width 10 ns. Obtained results show good laser-induced singleshot and multiple-shot damage threshold values for all studied co-crystals and are found up to 3.64 GW/cm 2 and 1.77 GW/cm 2 respectively.

show abstract

“…Materials can also be prepared by sequential synthesis/self-assembly techniques and by crystal growth including from solution, the melt and the vapor phase [97][98][99][100][101][102][103][104][105][106][107]; however, these approaches have not been as widely adapted to the fabrication of prototype devices as have electric field poling methods.…”

Section: Advances In Materials Processing and Characterizationmentioning

confidence: 99%

Theory-Guided Design of Organic Electro-Optic Materials and Devices

Dalton

Benight

2011

Polymers

View full text Add to dashboard Cite

Integrated (multi-scale) quantum and statistical mechanical theoretical methods have guided the nano-engineering of controlled intermolecular electrostatic interactions for the dramatic improvement of acentric order and thus electro-optic activity of melt-processable organic polymer and dendrimer electro-optic materials. New measurement techniques have permitted quantitative determination of the molecular order parameters, lattice dimensionality, and nanoscale viscoelasticity properties of these new soft matter materials and have facilitated comparison of theoretically-predicted structures and thermodynamic properties with experimentally-defined structures and properties. New processing protocols have permitted further enhancement of material properties and have facilitated the fabrication of complex device structures. The integration of organic electro-optic materials into silicon photonic, plasmonic, and metamaterial device architectures has led to impressive new performance metrics for a variety of technological applications.

show abstract

Configurationally locked, phenolic polyene organic crystal 2-{3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene}malononitrile: linear and nonlinear optical properties

Cited by 77 publications

References 30 publications

Molecular Origins of the High-Performance Nonlinear Optical Susceptibility in a Phenolic Polyene Chromophore: Electron Density Distributions, Hydrogen Bonding, and ab Initio Calculations

Molecular Origins of the High-Performance Nonlinear Optical Susceptibility in a Phenolic Polyene Chromophore: Electron Density Distributions, Hydrogen Bonding, and ab Initio Calculations

Organic noncentrosymmetric complexes of 4-nitrophenol for second harmonic generation

Theory-Guided Design of Organic Electro-Optic Materials and Devices

Contact Info

Product

Resources

About