Discotic Liquid Crystals.

Among the d10 coinage metal complexes, cyclic trinuclear complexes (CTCs) or trinuclear metallocycles with intratrimer metal-metal interactions are fascinating and important metal-organic or organometallic π-acids/bases. Each CTC of characteristic planar or near-planar trimetal nine-membered rings consists of Au(I)/Ag(I)/Cu(I) cations that linearly coordinate with N and/or C atoms in ditopic anionic bridging ligands. Since the first discovery of Au(I) CTC in the 1970s, research of CTCs has involved several fundamental areas, including noncovalent and metallophilic interaction, excimer/exciplex, acid-base chemistry, metalloaromaticity, supramolecular assemblies, and host/guest chemistry. These allow CTCs to be embraced in a wide range of innovative potential applications that include chemical sensing, semiconducting, gas and liquid adsorption/separation, catalysis, full-color display, and solid-state lighting. This review aims to provide a historic and comprehensive summary on CTCs and their extension to higher nuclearity complexes and coordination polymers from the perspectives of synthesis, structure, theoretical insight, and potential applications.

Coinage-Metal-Based Cyclic Trinuclear Complexes with Metal–Metal Interactions: Theories to Experiments and Structures to Functions

The association of the arene ruthenium metallacycle [Ru4(p-cymene)4(bpe)2(donq)2][DOS]4 (bpe = 1,2-bis(4-pyridyl)ethylene, donq = 5,8-dioxydo-1,4-naphtoquinonato, DOS = dodecyl sulfate) with pyreny...

https://pubs.acs.org/doi/pdf/10.1021/ja510338r

Designing supramolecular liquid-crystalline hybrids from pyrenyl-containing dendrimers and arene ruthenium metallacycles.

Chiral polycatenar 1H-pyrazoles self-assemble to form columnar mesophases that are stable at room temperature. X-ray diffraction and CD studies in the mesophase indicate a supramolecular helical organization consisting of stacked H-bonded dimers. The liquid-crystalline compounds reported are 3,5-bis(dialkoxyphenyl)-1H-pyrazoles that incorporate two or four dihydrocitronellyl chiral tails. It can be observed that the grafting of these branched chiral substituents onto the 3,5-diphenyl-1H-pyrazole core has a beneficial role in inducing mesomorphism, because isomeric linear-chain compounds are not liquid crystalline; this is not the usual scheme of behavior. Furthermore, the molecular chirality is transferred to the columnar mesophase, because preferential helical arrangements are observed. Films of the compounds are luminescent at room temperature and constitute an example of the self-organization of nondiscoid units into columnar liquid-crystalline assemblies in which the functional molecular unit transfers its properties to a hierarchically built superstructure.

Self-assembly in helical columnar mesophases and luminescence of chiral 1H-pyrazoles.

The use of liquid crystals for the fabrication of displays incorporated in technological devices (TVs, calculators, screens of eBook's, tablets, watches) demonstrates the relevance that these materials have had in our way of living. However, society evolves, and improved devices are looked for as we create a more efficient and safe technology. In this context, metallomesogens can behave as multifunctional materials because they can combine the fluidic state of the mesophases with properties such as photo and electroluminescence, which offers new exciting possibilities in the field of optoelectronics, energy, environment, and even biomedicine. Herein, it has been established the role of the molecular geometry induced by the metal center in metallomesogens to achieve the self-assembly required in the liquid-crystalline mesophase. Likewise, the effect of the coordination environment in metallomesogens has been further analyzed because of its importance to induce mesomorphism. The structural analysis has been combined with an in-depth discussion of the properties of these materials, including their current and potential future applications. This review will provide a solid background to stimulate the development of novel and attractive metallomesogens that allow designing improved optoelectronic and microelectronic components. Additionally, nanoscience and nanotechnology could be used as a tool to approach the design of nanosystems based on luminescent metallomesogens for use in bioimaging or drug delivery.

Advanced Functional Luminescent Metallomesogens: The Key Role of the Metal Center.

Silver pyrazolates with columnar liquid-crystal phases that are stable at room temperature have been prepared by reaction of silver nitrate with 3,5-diarylpyrazolates. The complexes consist of open-chain oligomers, despite the fact that the most common structural type for homoleptic coinage metal pyrazolates is the trimeric metallacycle [M(μ-pz)](3). The special characteristics of silver in forming reversible metal-ligand bonds in solution, evidenced experimentally, leads to supramolecular organizations in which the silver cations promote self-organization of the nonmesomorphic pyrazolates into helical 1D polymers that exhibit columnar mesophases. The materials are readily soluble in common organic solvents and are liquid-crystalline over a broader temperature range than their gold counterparts, which are known to form discrete cyclic trinuclear species. Thin films of the silver complexes show luminescence at room temperature. The compounds described here are the first examples of luminescent metallomesogens formed by a main-chain coordination polymer.

Silver Pyrazolates as Coordination‐Polymer Luminescent Metallomesogens

Several new cis-[RhCl(CO)2(Ln)] complexes have been prepared using different polycatenar pyrazole ligands (Ln) in order to obtain columnar liquid crystalline arrangements. The topology of the ligan...

Supramolecular structures and columnar mesophase induction in nondiscoid pyrazoles by complexation to rhodium(I)

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Silver Pyrazolates as Coordination‐Polymer Luminescent Metallomesogens

Supramolecular structures and columnar mesophase induction in nondiscoid pyrazoles by complexation to rhodium(I)