The control of luminous radiation has extremely important implications for modern and future technologies as well as in medicine. In this Review, we detail chemical structures and their relevant photophysical features for various groups of materials, including organic dyes such as metalloporphyrins and metallophthalocyanines (and derivatives), other common organic materials, mixed metal complexes and clusters, fullerenes, dendrimeric nanocomposites, polymeric materials (organic and/or inorganic), inorganic semiconductors, and other nanoscopic materials, utilized or potentially useful for the realization of devices able to filter in a smart way an external radiation. The concept of smart is referred to the characteristic of those materials that are capable to filter the radiation in a dynamic way without the need of an ancillary system for the activation of the required transmission change. In particular, this Review gives emphasis to the nonlinear optical properties of photoactive materials for the functi...

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation.

The impending breakdown in Moore s law has prompted the search for molecule-based information-processing components such as molecular switches and logic gates. Bistable molecules that afford states possessing distinct linear optical properties (absorbance, fluorescence) and that can be interconverted by chemical, redox, magnetic, or photonic stimuli have attracted considerable interest for Boolean logic operations. In principle, molecular computing could exploit ternary or higher-order digit representations, which would permit smaller device components. “Switchable” molecular properties are also of intense interest for sensor applications. Despite this interest, molecules that can exist in more than two stable and independently addressable states, which could be employed for complex and higher-order logic functions, have been explored significantly less than two-state molecules. One potentially very important procedure to exploit molecular switches is to utilize their cubic nonlinear optical (NLO) properties, and in particular their nonlinear absorption. However, this avenue is also poorly explored and is to date restricted to switching between three states at most, although such switching offers 1) the prospect of broadening the available spectral range (and in particular utilizing telecommunications-relevant wavelengths) and 2) the possibility of enhanced spatial control (compared to linear optical switching) because of the higher-order dependence on the intensity of the incident light. Herein we show that a specific binuclear metal alkynyl complex incorporating a functionalized 5,5’-dithienylperfluorocyclopentene (DTE) bridge can afford six stable and switchable states that possess distinct cubic NLO properties. The complex is comprised of independently addressable modules that respond orthogonally to protic (alkynyl ligandQvinylidene ligand), electrochemical (metal-centered redox: RuQRu), and photochemical (DTE ring-openingQring-closing) stimuli. The six states are interconverted along seven pathways, all of which result in distinct changes to cubic nonlinearity for specific regions of the spectrum. Our results demonstrate that complexes of this type have the potential to be used, among other things, in the construction of multi-input logic gates responding to diverse stimuli across a broad spectral range. The synthesis of the dinuclear ruthenium alkynyl complex oa(II) is depicted in Figure S1 in the Supporting Information. The DTE unit is obtained in the “open” form as its 5,5’diethynyl derivative; the open DTE is thermally stable, and this open form persists through the preparative steps that ultimately afford oa(II). Complete synthetic and characterization details are given in the Supporting Information. Complex oa(II) can be reversibly protonated to the di(vinylidene) complex ov(II), reversibly oxidized to the Ru complex dication oa(III), and photoisomerized with UV light to the closed alkynyl complex ca(II). Complex ca(II) can be reversibly protonated to cv(II) and reversibly oxidized to ca(III) and undergoes photoreversion to oa(II) on irradiation with red light. The vinylidene forms and the oxidized forms undergo reversible photoisomerization under analogous irradiation conditions. Note that oxidation of ruthenium vinylidene complexes with these coligands is an irreversible process, as assessed by cyclic voltammetry, so there is a maximum of six switchable states for this complex. The interconversions of the six stable states of the complex are depicted in Scheme 1, and key spectral data are tabulated in the Supporting Information (Table S1). Cyclic voltammograms and UV/Vis/NIR spectral progressions for the redox processes, the latter acquired with an optically transparent thin-layer spectroelectrochemical (OTTLE) cell and demonstrating stable isosbestic points, are given in the Supporting Information, together with NMR spectra demonstrating spectroscopically complete 1) photoisomerization between the open and closed forms and 2) protonation/deprotonation to afford the vinylidene and alkynyl complex forms, and IR spectra demonstrating spectroscopically complete oxidation from the Ru to the Ru form. Several organometallic alkyne-functionalized DTE complexes have been reported, and the effect of oxidation state on photochromic behavior has been probed, although there was no assessment of the effect of protonation/deprotonation on photochromism. [CpFe(h-C5H4C C DTE C C-hC5H4)FeCp] [11] and [(dppe)CpFe(C C DTE C C)FeCp[*] K. A. Green, Dr. M. P. Cifuentes, T. C. Corkery, Prof. M. G. Humphrey Research School of Chemistry, Australian National University Canberra, ACT 0200 (Australia) Fax: (+ 61)2-6125-0760 E-mail: mark.humphrey@anu.edu.au

Switching the cubic nonlinear optical properties of an electro-, halo-, and photochromic ruthenium alkynyl complex across six states.

https://cyberleninka.org/article/n/940497.pdf

The dendritic state

Coordination and organometallic complexes with second-order nonlinear optical (NLO) properties have attracted increasing attention as potential molecular building block materials for optical communications, optical data processing and storage, or electrooptical devices In particular, they can offer additional flexibility, when compared to organic chromophores, due to the presence of metal–ligand charge-transfer transitions, usually at relatively low-energy and of high intensity, tunable by virtue of the nature, oxidation state, and coordination sphere of the metal center This chapter presents an overview of the main classes of second-order NLO coordination and organometallic complexes with various ligands such as substituted amines, pyridines, stilbazoles, chelating ligands (bipyridines, phenanthrolines, terpyridines, Schiff bases), alkynyl, vinylidene, and cyclometallated ligands, macrocyclic ligands (porphyrins and phthalocyanines), metallocene derivatives, and chromophores with two metal centers The coverage, mainly from 2000 up to now, is focused on NLO properties measured at molecular level from solution studies, as well as on NLO properties of bulk materials

Coordination and Organometallic Complexes as Second-Order Nonlinear Optical Molecular Materials

Transition metal-containing macromolecules: En route to new functional materials

A combination of cyclic voltammetry (CV), UV−vis−NIR spectroscopy and spectroelectrochemistry, hyper-Rayleigh scattering (HRS) [including depolarization studies], Z-scan and degenerate four-wave mixing (DFWM) [including studies employing an optically transparent thin-layer electrochemical (OTTLE) cell to effect electrochemical switching of nonlinearity], pump−probe, and electroabsorption (EA) measurements have been used to comprehensively investigate the electronic, linear optical, and nonlinear optical (NLO) properties of nanoscopic π-delocalizable electron-rich alkynylruthenium dendrimers, their precursor dendrons, and their linear analogues. CV, UV−vis−NIR spectroscopy, and UV−vis−NIR spectroelectrochemistry reveal that the reversible metal-centered oxidation processes in these complexes are accompanied by strong linear optical changes, “switching on” low-energy absorption bands, the frequency of which is tunable by ligand replacement. HRS studies at 1064 nm employing nanosecond pulses reveal large non...

Electrochemical, spectroelectrochemical, and molecular quadratic and cubic nonlinear optical properties of alkynylruthenium dendrimers.

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Electrochemical, spectroelectrochemical, and molecular quadratic and cubic nonlinear optical properties of alkynylruthenium dendrimers.