NLO Molecules and Materials Based on Organometallics: Cubic NLO Properties

Humphrey, Mark G.; Cifuentes, Marie P.; Samoć, Marek

doi:10.1007/978-3-642-01866-4_2

Cited by 15 publications

(3 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In parallel to studies devoted to Fc-containing redox assemblies, redox-active electron-rich organometallic acetylides of the group 8 metals (iron and ruthenium in particular) have been demonstrated to possess a strong potential for the reversible storage of information at the molecular level. − For instance, in the field of optics, the high stability of these compounds under several redox states allows for simple electrochemical generation of families of highly polarizable compounds exhibiting widely different electronic transitions in the different redox states, which also translate into widely different linear and nonlinear optical properties. − Moreover, in contrast to most organic derivatives, their peculiar redox chemistry offers a unique possibility for reversible redox-switching between these states. Thus, several groups have shown that ruthenium-containing representatives of such molecules when covalently anchored on (semi)conducting surfaces, such as halogenated silicon , and gold, − exhibited a molecular conductance which could be electrochemically gated.…”

Section: Attachment Of Bistable Redox Moleculesmentioning

confidence: 99%

Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies

2016

View full text Add to dashboard Cite

This review provides a comprehensive survey of the derivatization of hydrogen-terminated, oxide-free silicon surfaces with electroactive assemblies (from molecules to polymers) attached through strong interactions (covalent, electrostatic, and chimisorption). Provided that surface modification procedures are thoroughly optimized, such an approach has appeared as a promising strategy toward high-quality functional interfaces exhibiting excellent chemical and electrochemical stabilities. The attachment of electroactive molecules exhibiting either two stable redox states (e.g., ferrocene and quinones) or more than two stable redox states (e.g., metalloporphyrins, polyoxometalates, and C60) is more particularly discussed. Attention is also paid to the immobilization of electrochemically polymerizable centers. Globally, these functional interfaces have been demonstrated to show great promise for the molecular charge storage and information processing or the elaboration of the electrochemically switchable devices. Besides, there are also some relevant examples dealing with their activity for other fields of interest, such as sensing and electrochemical catalysis.

show abstract

Section: Attachment Of Bistable Redox Moleculesmentioning

confidence: 99%

Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies

2016

View full text Add to dashboard Cite

show abstract

“…Focus on materials science research is slowly but steadily shifting from inorganic and organometallic systems to organic materials. − Interest in organic materials has been increasing gradually due to their design flexibility, low molecular weight, low cost, and ecofriendly nature. , Certain classes of organic compounds in their solid-state respond to external stimuli and find myriad of applications in optoelectronics, nonlinear optics (NLO), ferroelectrics, semiconductors, etc. − However, most of these properties demand not only the presence of non-centrosymmetric phases but also the existence of polar phases of the materials in their crystalline form. But controlling the non-centrosymmetric phase remains a key challenge for designing such materials. − While crystal symmetry is mainly governed by the molecular packing in the crystal lattice, external parameters such as crystallizing solvents, pressure, thermal stimuli, etc.…”

Section: Introductionmentioning

confidence: 99%

Concomitance, Reversibility, and Switching Ability of Centrosymmetric and Non-Centrosymmetric Crystal Forms: Polymorphism in an Organic Nonlinear Optical Material

Jha

Dutta

Munshi

2017

Crystal Growth & Design

View full text Add to dashboard Cite

Reversibility between two concomitant polymorphs and their switching ability is demonstrated for the novel organic nonlinear optical (NLO) material Z-3-(3-methoxyphynyl)-2-(4-nitrophenyl)acrylonitrile. The appearances of their concomitant as well as exclusive polymorphic forms were discovered upon systematic crystallization experiments using various solvents. Determination of X-ray crystal structures confirmed that the polymorphs crystallize in centrosymmetric (P21/n) and non-centrosymmetric (Fdd2) space groups. A search using the Cambridge Structural Database revealed that there exist only 10 such polymorphic pairs. Reversible phase transitions and the switching ability between the polymorphs can be achieved via both heat and solvents as stimuli. Structural analysis confirmed that the polymorphs have two-dimensional similarity. Further, quantitative and qualitative analysis of interaction energies based on the UNI force field and energy frameworks indicate that they possess very similar energies, although the centrosymmetric form is slightly lower in energy. A comparably high value of second harmonic generation activity and the NLO properties as estimated based on gas-phase and in-crystal calculations suggest that the non-centrosymmetric form could be a potential NLO material. To the best of our knowledge, this study is the rarest of its kind to show the reversibility and switching ability between centrosymmetric and non-centrosymmetric polymorphic phases in an organic material, induced via both thermal and solvent stimuli.

show abstract

“…It is becoming increasingly apparent that the incorporation of additional metallic fragments within the conjugated pathway of organometallic complexes offers many avenues for fine-tuning of electronic structure, and therefore function, that cannot be readily attained with organic structures alone. − Metal complexes are now finding application in targeted materials as a consequence of this capacity to fine-tune the properties of the metal–ligand assembly. Some of these approaches incorporate ligand architectures into polymers, provide dynamically porous materials, guide the construction of surface-based catalysts, and modulate the properties of nonlinear optical materials. , …”

Section: Introductionmentioning

confidence: 99%

Coordinating Tectons. Experimental and Computational Infrared Data as Tools To Identify Conformational Isomers and Explore Electronic Structures of 4-Ethynyl-2,2′-bipyridine Complexes

Mackenzie¹,

Bock²,

Lim³

et al. 2017

Organometallics

View full text Add to dashboard Cite

4-Ethynyl-2,2'-bipyridyl substituted ruthenium alkynyl complexes have been prepared and used to access a range of binuclear homo-metallic ruthenium and hetero-metallic ruthenium-rhenium complexes. These have been characterized by a variety of spectroscopic and single-crystal X-ray diffraction experiments. The IR spectra of a number of these ruthenium alkynyls display multiple ν(C≡C) bands in the IR spectra, which are rationalized in terms of putative conformational isomers, whose calculated infrared stretching frequencies are comparable to those obtained experimentally. The mononuclear alkynyl complexes Ru(C≡C) undergo reversible one electron oxidations centered largely on the alkynyl ligands as inferred from the significant shift in ν(C≡C) frequency on oxidation, whilst the binuclear complex [Ru{C≡C-4bpy-κ 2-N,N'-RuClCp}(dppe)Cp*] + undergoes initial oxidation at the very electron rich {RuCl(bpy)Cp} fragment causing only a small change in ν(C≡C). A combination of IR and UV-vis spectroelectrochemical experiments, supported by quantum chemical calculations on a selected range of conformers, led to the classification of [Ru{C≡C-4-bpy-κ 2-N,N'-RuClCp}(dppe)Cp*] + as a weakly Class II mixed valence compound (H ab = 306 cm-1). These results indicate that there is improved electronic communication through the 4-ethynyl-2,2'-bipyridyl ligand compared to the analogous 5-ethynyl-2,2'-bipyridyl complexes (H ab = 17 cm-1).

show abstract

NLO Molecules and Materials Based on Organometallics: Cubic NLO Properties

Cited by 15 publications

References 38 publications

Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies

Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies

Concomitance, Reversibility, and Switching Ability of Centrosymmetric and Non-Centrosymmetric Crystal Forms: Polymorphism in an Organic Nonlinear Optical Material

Coordinating Tectons. Experimental and Computational Infrared Data as Tools To Identify Conformational Isomers and Explore Electronic Structures of 4-Ethynyl-2,2′-bipyridine Complexes

Contact Info

Product

Resources

About