Clamshell-type bis-phthalocyanines as colour-changing optical limiters: TDDFT modelling of electrically induced absorption for real-time colour indication of optical limiter efficiency in nonlinear laser protection.

This paper presents an innovative method for assessing the performance of optical limiters, which are devices that protect humans against laser radiation. The essence of the process is that with increasing laser radiation intensity, the colour of nonlinear absorbers, the working components of these devices, can change in contrast to the original one, which was demonstrated by quantum-chemical linear response time-dependent density functional theory (LR-TDDFT) for molecules excited by static electric finite fields (FF) within the general DFT (density functional theory) approach. Modelling was carried out on clamshell-type bis-phthalocyanines, in which the macrocycles are strapped by a cyclotriphosphazene spacer, suitable candidates for creating nonlinear optical (NLO) dyes for laser technology. As calculations have shown, acting as a "litmus test", these incredibly stable macrocyclic compounds are not only capable of providing laser protection but also give a real-time visual indication of the protection through changes in the colour of the dye, which correlate with different levels of laser power. Such indication can visually show the current state of optical limiters in practice, allowing users to easily determine whether the limiter material provides adequate protection or already requires replacement. A modelling protocol and program code for calculating the colour of a substance based on its absorption spectrum are presented.

Conditions for the efficiency of optical limiting based on experiment and quantum chemical calculations.

The development of suitable protection against laser radiation has proven challenging due to the lack of predictive models. The purpose of this article is to exclude the existing drawback by creating a universal strategy based on correlations between experimental and theoretical data characterizing the nonlinear optical properties of absorbers, for which a series of low-symmetry penta(chloro)cyclotriphosphazene-substituted monophthalocyanines was chosen. To search for correlations on a small series of dyes, we used the advanced algorithm CORRELATO, which has been proven to construct even the most unusual relationships demonstrated in our previous works. Due to the reducing symmetry of molecules, large values of the nonlinear absorption coefficient (more than 3000 cm GW-1) and, as a result, wide dynamic ranges (up to 630) with a high degree of attenuation of nanosecond laser radiation (10-20 times) were achieved. The use of the finite-field DFT method has allowed the calculation of dipole moments, polarizabilities and hyperpolarizabilities. The numerical data obtained during the calculations were used in correlations of theory vs. experiment to derive mathematical expressions (inequalities) to assess the effectiveness of absorbers in limiting the power of laser radiation.

A New Way to Predict the Efficiency of Optical Limiters without Providing an Experiment: Processing of TDDFT Calculations for the Case of Pure Two-Photon Absorption.

Laser-power-limiting devices play a predominant role in photonics because of their potential for protecting human eyes and optical devices that are sensitive to intense laser beams. This paper describes a new methodology for predicting the efficiency of optical limiting based on electric-field-induced changes in absorption spectra calculated with the TDDFT quantum-chemical method. Analytical equations are derived to evaluate the optical thresholds and speed of switching on, the dynamic range, and the degree of nonlinear attenuation of the radiation fluxes for the case of two-photon absorption. Thus, the researcher does not need to conduct costly experiments to evaluate the suitability of nonlinear absorbers for the creation of optical limiters. The possibility of developing a forecasting model is demonstrated by an example of a series of stable slipped-cofacial phthalocyanine J-type dimers, which were synthesized and investigated previously.

Aggregation of slipped-cofacial phthalocyanine J-type dimers: Spectroscopic and AFM study.

Direct metallation of 2-hydroxyphthalocyanine J-type slipped-cofacial dimeric ligand by Mg, Zn, Cu, Ni and Co salts has been carried out to obtain corresponding metal complexes selectively without any noticeable dissociation or polymerization of the starting ligand. Integrated analysis of aggregation properties in the synthesized series has been conducted with the involvement of AFM microscopy, UV/Vis spectroscopy and theoretical assessment. As a result, a nonlinear relationship between absorption and concentration was found, with aggregation beginning to appear at concentrations above 3.3 × 10-5 mol L-1 with predominant formation of trimers from the dimeric molecules in THF solutions.

Threshold concentration in the nonlinear absorbance law.

A new nonlinear relationship of the absorption coefficient with the concentration was proposed, allowing the calculation of the threshold concentration, which shows that there is a deviation from the Beer-Lambert law. The nonlinear model was successfully tested on a stable dimeric phthalocyanine ligand of J-type in solvents with different polarity. It was shown that deviation from the linearity is connected with a specific association of the macrocyclic molecules, which, in the case of non-polar solvents, leads to the formation of H-aggregates composed of J-type dimeric molecules. The aggregation number was estimated to be less than 1.5, which has allowed us to conduct a series of analytical experiments in a wide range of concentrations (1 × 10-6-5 × 10-4 mol L-1).

Thermally stable J-type phthalocyanine dimers as new non-linear absorbers for low-threshold optical limiters.

The possibility of developing new advanced optical limiters of laser radiation at 532 nm with low limiting thresholds has been demonstrated on thermally stable phthalocyanine J-type dimeric complexes of Mg, Zn, Cu, Ni, and Co. A new "threshold" model based on radiative transfer phenomena in nonlinear optical media was suggested for the exact definition of nonlinear absorption coefficient ß and optical limiting threshold Ic. This model allows the determination of the optical characteristics of the limiter in the same active material with layers of different thicknesses, as well as the use of different parameters of laser radiation, such as cross-sectional spatial profiles of the laser beam and shapes of the laser pulse over time. The maximum value of the nonlinear absorption coefficient (ß = 360 cm GW(-1)) and the lowest limiting threshold (Ic = 0.03 J cm(-2)) were estimated for a J-type zinc phthalocyanine dimer.

meso-Phenyltetrabenzotriazaporphyrin based double-decker lanthanide(III) complexes: synthesis, structure, spectral properties and electrochemistry.

A series of half-sandwich and sandwich-type lanthanide(III) complexes have been prepared using tetrabenzotriazaporphyrin ligands. Reaction of 27-phenyl-29H,31H-tetrabenzo[b,g,l,q][5,10,15]-triazaporphyrin (PhTBTAPH2, 1) with salts [LnX3]·nH2O (Ln = Eu (a), Lu (b); X = OAc, acac) afforded the single- and homoleptic double-deckers (PhTBTAP)LnOAc (2) and (PhTBTAP)2Ln (3) respectively. Heteroleptic double-decker compounds (PhTBTAP)LnPc (4a,b) were obtained upon interaction of 1 with the corresponding Ln mono(phthalocyaninates). An unexpected formation of partially and completely dephenylated co-products 5 and 6 has been detected in the synthesis of sandwich 3, while the possibility of the dearylation of the half-sandwich compound 2 has been demonstrated as well. A more predictable yet firstly observed formation of the triple-decker compound (PhTBTAP)3Eu2 (7) has also been found. Structural studies of 3 supported by 1H NMR spectra, XRD analysis and DFT theoretical calculations reveal that the Eu complex 3a is formed as a single isomer, while the lutetium compound 3b represents an inseparable mixture of two rotational isomers with virtually identical spectral characteristics. The double-decker compounds 3 and 4 reveal intrinsic UV-Vis/NIR absorption as well as peculiar electrochromic behavior. The heteroleptic derivatives 4 generally show intermediate spectral and electrochemical properties with respect to their homoleptic relatives.

Sandwich double-decker lanthanide(III) "intracavity" complexes based on clamshell-type phthalocyanine ligands: synthesis, spectral, electrochemical, and spectroelectrochemical investigations.

Phthalocyanine compounds of novel type based on a bridged bis-ligand, denoted "intracavity" complexes, have been prepared. Complexation of clamshell ligand 1,1'-[benzene-1,2-diylbis(methanediyloxy)]bis[9(10),16(17),23(24)-tri-tert-butylphthalocyanine] ((clam,tBu)Pc(2)H(4), 1) with lanthanide(III) salts [Ln(acac)(3)]⋅n H(2)O (Ln = Eu, Dy, Lu; acetylacetonate) led to formation of double-deckers (clam,tBu)Pc(2)Ln (2 a-c). Formation of high molecular weight oligophthalocyanine complexes was demonstrated as well. The presence of an intramolecular covalent bridge affecting the relative arrangement of macrocycles was shown to result in specific physicochemical properties. A combination of UV/Vis/NIR and NMR spectroscopy, MALDI-TOF mass-spectrometry, cyclic voltammetry, and spectroelectrochemistry provided unambiguous characterization of the freshly prepared bis-phthalocyanines, and also revealed intrinsic peculiarities in the structure-property relationship, which were supported by theoretical calculations. Unexpected NMR activity of the paramagnetic dysprosium complex 2 b in the neutral π-radical form was observed and examined as well.