Transition metals induce control of enhanced NLO properties of functionalized organometallic complexes under laser modulations

The molecular engineering of organometallic complexes has recently attracted renewed interest on account of their potential technological applications for optoelectronics in general and optical data storage. The transition metal which induces control of enhanced nonlinear optical properties of functionalized organometallic complexes versus not only the intensity but also the polarization of the incident laser beam is original and important for all optical switching. This makes organometallic complexes valuable and suitable candidates for nonlinear optical applications. In the present work, we report the synthesis and full characterization of four organometallic complexes consisting of N, N-dibutylamine and azobenzene fragments but differ by auxiliary alkynyl ligands or metal cations. Thus, a ferrocenyl derivative 1 and three ruthenium complexes 2–4 have been prepared. The nonlinear optical properties of the four new azo-based ruthenium and iron organometallic complexes in the solid state, using polymethylmethacrylate as matrix, have been thoroughly studied. This concept is extended to computing the HOMO and LUMO energy levels of the considered complexes, dipole moment, first and second order hyperpolarizabilities using the 6–31 + G(d,p) + LANL2DZ mixed basis set. The second and third nonlinear optical properties of the resulting polymer composites were obtained by measuring SHG and THG response by means of the Maker fringe technique using a laser generating at 1,064 nm with a 30 ps pulse duration. The values of the second and third order NLO susceptibilities of the four organometallic complexes were found to be higher than the common references used. Theoretical calculation shows that the large first and second order hyperpolarizablities are caused by strong intramolecular charge transfer between the transition metal parts and the ligands though a conjugated transmitter. These results indicate that the present organometallic complexes are valuable candidates for optoelectronic and photonic applications.

Scientific Reports | (2020) 10:15292 | https://doi.org/10.1038/s41598-020-71769-2 www.nature.com/scientificreports/ of functional materials [13][14][15] . Moreover it could be also useful for tuning the properties of organometallic based magnetics for spintronic and quantum computing devices 16 and also electronic and optical properties for photovoltaic and optoelectronic applications 17 . Much research has been carried out on the study of azobenzene derivatives which, thanks to their reversible and stable trans-cis photoisomerisation over many cycles, are among the most studied photochromic compounds in recent years. Azobenzene systems possess also obvious advantages in the field of NLO, due to their high intramolecular charge transfer and their high hyperpolarizabilities [18][19][20] which can be coupled with the photoinduced trans-cis isomerization. Hence, they could function as NLO molecular switches by applying light of different wavelengths to obtain varying amounts of cis and trans isomers. On the other hand, donor-acceptor substituted azo dyes, which are molecules with easily polarizable electrons, show large second-order nonlinearities 21,22 . A major advantage is also the possibility of inducing a noncentrosymmetric structure within the material, for example by orientation by the Corona poling technique, because obtaining macroscopic quadratic NLO properties requires breaking the centrosymmetry of the medium by orientation of the chromophores. These properties of azobenzene derivatives give the possibilities of many applications in optical switching and data storage 23,24 .
We report herein the synthesis and full characterization of four new azo-based ruthenium and iron organometallic complexes. The nonlinear optical (NLO) responses of these complexes, related to metal acetylide complexes, have been evaluated by means of second and third harmonic generations (SHG, THG) experimental techniques and also quantum chemical calculations. We undertook this study to better understand the physical contribution of the metal center and its coordination sphere to the NLO susceptibilities of the complexes. The parameters responsible for second and third-order nonlinear-optical effects such as second and third harmonic generation are the first and second order hyperpolarizabilities. A conventional key to achieving high values of these parameters in metal acetylide complexes is to lengthen the π-conjugate system and strengthen the donor-acceptor character 21,[25][26][27][28][29][30] . In this work the effect of the metal transition complexation on the intramolecular charge transfer as well as the role of auxiliary ligands have been investigated. The relations between theoretically calculated NLO properties and the experimental obtained second and third order susceptibilities are presented. Both results indicate that these molecular materials are valuable candidates for application in optoelectronics and photonics 31 .
Flash column chromatography was performed on silica gel (high-purity grade, 230-400 mesh, 40-63 μm, Sigma-Aldrich) according to a standard technique. Nuclear magnetic resonance spectra ( 1 H, 13 C and 31 P) were recorded on a Bruker spectrometer (400 MHz). Chemical shifts for 1 H and 13 C spectra are recorded in parts per million and are calibrated to solvent residual peaks (for example: CHCl 3 : 1 H 7.26 ppm, 13 36 were dissolved in 20 mL of THF and 20 mL of Et 3 N in a round bottom flask. This flask was purged three times with argon. 11 mg (60 μmol) of copper iodide and 41 mg (60 μmol) of bis(triphenylphosphine)palladium(II) dichloride were added and the reaction mixture was stirred overnight at 50 °C. After the solvent was removed, the residue was extracted 3 times with 25 mL of CH 2 Cl 2 and washed with 50 ml of water, and then dried over Na 2 SO 4 . The resulting mixture was concentrated under reduced pressure. The crude product was purified by chromatography on silica gel eluted with ether/petroleum ether (1/4, v/v) to give 1. Red-orange crystalline powder, yield 366 mg, 59%. 1 (25 mL) and stirred for 16 h. The dark red solution was filtered and the solvent removed in vacuo. The solid residue was washed with deoxygenated diethylether (3 × 10 mL) to remove any excess of 6 and then redissolved in CH 2 Cl 2 , and K 2 CO 3 (0.6 mmol) was added to the vinylidene solution ( 31 P{ 1 H}NMR: δ (ppm) -16.7 (s, PPh 2 )) and the stirring continued for a further 2 h. The resulting red-orange solution was filtered before 20 ml of heptane was added. The solid thus obtained was isolated by filtration, washed with pentane, and dried under vacuum to give the product as a red-orange crystalline powder. Complex 2, yield 163 mg, 60%. 31 (2 mmol) was added and the reaction mixture was stirred for another 6 h. The crude product was purified by chromatography on silica gel eluted with CH 2 Cl 2 /petroleum ether (1/2, v/v) to give a red-orange solid identified as 3. Yield 130 mg, 45%. 31

Electrochemical experiments.
Electrochemical experiments were carried out with a Biologic SP-150 potentiostat driven by the EC-Lab software including ohmic drop compensation. Cyclic Voltammetry (CV) was performed in a three-electrode cell controlled at a temperature of 293 K in a glove box containing dry, oxygen-free (< 1 ppm) argon. Working electrodes were glassy carbon planar disk electrodes (Ø = 3 mm). Counter electrodes were platinum wires. Reference electrodes were Ag/AgNO 3 (0.01 M CH 3 CN). Experiments were recorded in dry HPLC-grade acetonitrile with tetrabutylammonium hexafluorophosphate (Bu 4 NPF 6 , electrochemical grade, Fluka) as supporting electrolyte. All the potential reported were calibrated versus ferricinium/ ferrocene couple (Fc + /Fc) (IUPAC Recommendation) 39 . Based on repetitive measurements, absolute errors on potentials were found to be around ± 5 mV.

Preparation of host-guest films of complexes and optical absorption measurements.
For the host-guest films preparation, the various chromophores and PMMA (Sigma-Aldrich, Mw = 15,000 g/mol) have been dissolved in dichloromethane at concentration of 50 g/L. The concentration of the compounds was 100 µmol towards 1 g of PMMA. The solutions were deposited using the spin-coater (SCS G3) at 1,000 rpm on BK 7 glass plates substrates with 1 mm thickness (which were cleaned in distilled water using ultrasonic bath, acetone, and ethanol) and then were dried. Obtained guest-host polymer films were kept at room temperature during two days in order to eliminate any remaining of solvent. The thickness of deposited films was calculated by the profilometer (Dektak 6M, Veeco).
We used Lambda 950 UV/Vis/NIR spectrophotometer (PerkinElmer) with the range 300-1,200 nm in order to measure the absorption spectra of the samples.

NLO studies SHG and THG measurements.
After the preparation of the thin films, we used the corona poling technique in order to orientate the chromophores at the thin layer surface. First, they were heated on a hot plate at selected poling temperature of 100 °C. Then an external electric field was provided by applying a voltage of + 5 kV to a tungsten needle fixed at 1 cm above the polymer surface, while the electrode under the glass substrate was grounded. With the remaining electric field, the heater was switched off, and the sample was cooled down to room temperature, the corona field was turned off.
In order to evaluate the nonlinear optical response of our metal complexes 1, 2, 3 and 4, we use the Third and Second Harmonic Generation (SHG & THG), which are based on the Maker Fringe technique 40 . In this Harmonic Generation technique, an incident laser beam at the frequency ω interacts with a nonlinear medium in order to generate another beam with double and triple frequencies.
We used a Nd:YAG laser working at 1,064 nm with 30 ps pulse duration and we employed 10 Hz repetition rate (Fig. 1). The input energy of laser pulses was controlled by laser power/energy meter (LabMax TOP, COHER-ENT) to be 95 μJ for SHG and 140 μJ for THG measurements respectively. The thin films were mounted on a rotating stage and the beam was focalized on them. A fast photodiode measured a portion of the input beam in order to synchronize the rotation and the fundamental beam. The interference filter at 532 nm (or 355 nm) was used to select the desired wavelength of light 20,[41][42][43][44] and was used to cut the pump beam before the photomultiplier, that allowed the third harmonic or the second harmonic generated signal to be detected. The polarization of second and third harmonic was controlled by polarizer placed before the photomultiplier. We used established Theoretical quantum chemical calculations of NLO properties. For nonlinear optical properties calculation of the first and second order hyperpolarizabilities (β, γ), the time-dependent Hartree-Fock (TDHF) level of theory with functional LanL2DZ for transition metals Ru Fe and 6-31 + G(d,p) functional for the other concerned atoms (C, H, N, P, Cl) have been used. Indeed, in order to obtain good theoretical results we combined two methods (LANL2DZ functional 46 for transition metals and all-electron basis sets for all other non-transition-metal atoms), which is prevalent in computations for transition-metal-containing complexes.
In order to get a precise estimation of the hyperpolarizabilities one should take into account d polarization functions on the carbon and nitrogen atoms and the addition of p functions on hydrogen atoms and diffuse functions. Calculations were performed for structures optimized by density functional theory DFT/B3LYP at the 6-31 + G(d,p) + LANL2DZ mixed basis set. The hybrid-GGA functional B3LYP 47 gives the best performance in predicting the good structure and HOMO, LUMO properties. All calculations were done using GAUSSIAN 09 program package.
These new alkynyl complexes were characterized by MS or satisfactory microanalyses, UV-vis spectroscopy and 1 H-, 31 P-and 13 C-NMR spectroscopy (see part 1.1 and Supporting Information).
Cyclic voltammetry. In order to gain insight into the electronic environment of the metal atom in the new alkynyl complexes, the electrochemical properties of these compounds were measured by means of cyclic voltammetry in 0.1 M tetra-butylammonium hexafluorophosphate ([n-Bu 4 N]PF 6 ) methylene chloride solutions. The results are summarized in Table 1. The cyclic voltammetric scan of compound 1 exhibits one reversible oxidation wave that corresponds to the ferrocene oxidation with a half wave potential of E 1/2 = 0.10 V (vs. FeCp 2 / FeCp 2 + ). This value can be compared to that of free ferrocene (i.e. internal reference used for calibration), which clearly reveals an electron transfer from donor ferrocene to the ethynyl unit, which behaves as a modest electron with-drawing group: the oxidation of the iron center becomes more anodic compared to free ferrocene due to the removal of electron density. A second anodic wave is observed at E 1/2 = 0.50 V. This wave is reversible  ). The lowest potential oxidation waves are attributed to the one electron oxidation of the ruthenium centers. These observations are consistent with previous results 50,51 . Conversely, the highest oxidation potentials are attributed to the azo-dialkylamino fragment.
The cyclic voltammograms of the acetylide compound 4 shows a reversible oxidation wave (I pa /I pc ≅ 1), corresponding to the Ru II/III couple at a potential [E 1/2 = − 0.05 V vs. FeCp 2 /FeCp 2 + ] which is concordant with the data mentioned for RuX(PPh 3 ) 2 (η 5 -C 5 H 5 ) series 52 . A second reversible oxidation wave is observed at E 1/2 = 0.25 V, that would correspond to the waves observed in 2 and 3, that we attributed to the oxidation of the azo-dialkylamino fragment. Surprisingly, a third wave, quasi reversible, was observed at 0.5 V vs. FeCp 2 /FeCp 2 + . This wave was tentatively attributed to a further oxidation of the azo-dialkylamino fragment to two-electron oxidation products 51,53 . Photochemical studies in solution and in solid state. The UV-vis absorption spectra of the azo-ethynyl complexes 1-4 were recorded in dichloromethane, and the absorption data of these compounds are listed in Table 2. The ferrocenyl compound 1 (Fig. 5) shows a wide and strong absorption band between 390-530 nm, presumably due to superimposed π-π* and d-d transition arising from the ferrocene moiety [54][55][56][57] , together with the n-π* and π-π* absorption bands of the azobenzene chromophore.    Table 1 and presented in Fig. 5. They are very similar with those of parent compounds mentioned in the literature.
The UV-vis spectrum of complex 2 contains a broad low energy non-symmetrical absorption band with a maximum centred around 514 nm. This low energy band is accompanied by a smooth shoulder at 400 to 430 nm with can be consistent with the π-π* absorption bands of the ethynyl-azo unit as observed in trans-[RuCl(-C⋮C-R)(dppe) 2 ] 14 , that overlaps with MLCT bands of the metal-acetylide unit.
The UV-vis spectra for the alkynyl-metal complex 4 shows a broad absorption band from 380 to 550 nm, that would correspond to the superimposition of both a MLCT band around 400 nm, that is concordant with the data mentioned for other Ru(-C⋮C-R) (PPh 3 ) 2 (η 5 -C 5 H 5 ) (R = H, CHO) complexes 52 , and the π-π* absorption bands of the azobenzene chromophore, as observed in the previous compounds.
The UV-Visible absorption spectra of the four investigated metal complexes dissolved in dichloromethane and then embedded in PMMA films at the concentration 100 µmol/g are given in Fig. 6. The spectra of the obtained films exhibit wide absorption band with maximum at 464 nm, 500 nm, 514 nm, and 481 nm respectively for the films of complexes 1, 2, 3 and 4 which correspond to ligand centered (LC, π-π* and n-π*) transitions 58 . They are absolutely similar to the absorption spectra obtained for the four investigated metal complexes dissolved in dichloromethane. More interestingly for the measurements of SHG and THG, we observed that the samples show high optical transparency, at the wavelengths higher than 700 nm.

SHG and THG responses. The measurements of SHG and THG of compounds 1, 2, 3 and 4 in PMMA
films at the concentration 100 µmol/g, were obtained by using the Maker fringe technique for s-and p-polarized fundamental beam. We used the corona poling just before starting the measurements in order to increase a uniaxial orientation of the molecules and consequently enhance the 2nd order NLO properties of the compounds in the polymer films. The obtained SHG response is due to the break of the centrosymmetry of the studied organometallic complexes. Figure 7 represents the dependence of the second harmonic intensity generated as a function of the incident angle. As shown in this figure, the four films have a maximum signal between 60° and 65° and zero intensity at normal incidence of the fundamental beam. The intensity depends on the polarization p or s. In our case, the polarization of the second harmonic signal was found to be always p-polarized regardless the incident polarization.
For the calculation of the quadratic NLO susceptibilities, we used the comparative model of Lee and coworkers which compares the intensities of SHG for films and for quartz plate which is expressed by the following equation and which takes into account the linear optical absorption 59 .
where χ (2) Quartz = 1.0pm/v is the quadratic susceptibility of quartz, l coh Quartz is the coherent length of quartz, α is the absorption coefficient at doubled laser wavelength, d is the film thickness, I 2ω and I 2ω Quartz are the SHG intensities for the sample and quartz respectively under the same conditions of measurement. The obtained quadratic NLO susceptibilities for 1-4 films are presented in Table 2. For the input-output values of χ (2) were found to be www.nature.com/scientificreports/ higher at polarization p-p than polarization s-p, which is caused by the symmetry peculiarities of the guest-host polymeric films after poling. On the basis of these results ( Table 2) the film of complex 4 was found to exhibit higher second-order optical nonlinearity than the three other films. This result might be due to different polarity and hence different charge transfer from the metal to the π-conjugated acetylide azobenzene system (MLCT) in complex 4 as compared with the other two ruthenium metal complexes. This is intrinsic to the presence of bipyridine (3) or cyclopentadienyl (4) pi-acceptor ligands, whereas the dppm (2) and PPh 3 ligands are sigma-donor Silica is the cubic susceptibility of silica, l coh Silica is the coherent length of silica, α is the absorption coefficient at triple laser wavelength, d is the film thickness, I 3ω and I 3ω Silica are the THG intensities of the samples and silica at the same conditions, respectively. The Fig. 8 represents the dependences of the third harmonic intensity generated as function of the incident angle.
The calculated values of χ (3) for 1-4 films are given in Table 2. We have the same results before and after corona poling which is expected as the orientation has no significant influence on third-order NLO properties. Due to the extended π-conjugated chain complexes and coupling between the metal 61 and the remote groups through the π -conjugated path of the investigated metal complexes, the third-order nonlinear optical susceptibilities values of χ (3) ( Table 2) are stronger than the one of the silica 62 . The complex 1 is characterized with a higher third order NLO susceptibility than 2, 3 and 4 due to more effective electronic delocalization which is caused by charge transfer from the (N,N-dibutylamine) and ferrocenyl donor groups to the azo accepting unit. from third order susceptibility (Table 2) and taking into account the concentration of the complexes and the local field factor, we calculated the electronic contribution of second hyperpolarizability γ elec and we found that third order susceptibility, γ elec for 1 is also much higher than the other complexes 62,63 .
Although the experimental methods used in the literature to determine the χ (2) and χ (3) susceptibilities are slightly different, a comparison between the performances of our four organometallic complexes 1-4 and the ones reported for the state-of-the-art SHG/THG compounds could be made. However we have to underline here that for the third harmonic generation as we investigate thin film so what we are measuring is electronic contributions which is not the case for example for degenerate four waves mixing but comparison could be done. From Table 3, we can clearly see that the χ (3) susceptibility values are slightly lower in the case of our organometallic complexes while the χ (2) susceptibility values are generally much higher for our complexes 1-4. Thus, the sizeable SHG response for the complexes 1 and 4 indicates that these compounds are valuable candidates for potential applications in NLO and more specifically, for the evolution towards applications in molecular electronics and photonics and in related fields including second-order optical effects in organometallic compounds induced by an acoustic field 26,64 . Considering third harmonic generation, electronic contributions were measured as we investigated thin films. This is obviously a difference with results previously reported by using the degenerate four waves mixing approach 65-71 . Hyperpolarizabilities and HOMO, LUMO analysis. To engineer optimal nonlinear optical properties, the origins of the nonlinear optical phenomena must be understood. This requires knowledge of the bonding properties of the atoms in the molecules. To understand the connection between molecular structure and NLO property, we have to expand the scope of our investigation to include the computing the first and second order  Tables 4, 5. The β tot value has been calculated using the following expression 73 .
Generally, an increase in the β value occurs together with the hypsochromic shift effect (see Table 4) what is seen for compounds 1 and 4. Theoretical results suggest that better second order hyperpolarizabillities possess the ferrocenyl compound 1 and the ruthenium metal complex 4. These results are in good agreement with the experimental results, where the best χ (2) were obtained for molecules 1 and 4. The HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) are very important aspects to consider the NLO properties. In general if the HOMO-LUMO gap decreases (molecule 2-3), thus causing a bathochromic  www.nature.com/scientificreports/ shift the NLO properties should increase. In our case, there is no such relationship because absorption bands for molecules 2, 3 are close to resonance and the second harmonic signal can be partially absorbed.
The calculated hyperpolarizabilities of these molecules were compared with first order hyperpolarizabilities of other organometallic compounds (see Table 4 30,74 ). The study reveals that the investigated complexes have the same β range as other organometallics complexes known in literature hence in general may have potential applications in the development of non-linear optical materials.
The average second-order hyperpolarizability γ tot values have been calculated using the following formula: The calculated second order hyperpolarizability tensor components are presented in Table 5. The hyperpolarizability of γ tot obtained for molecules 1-4 are quite large comparable to the values obtained for other organometallic materials as presented in Table 5 30,61 . The second order frequency-dependent hyperpolarizability for compound 1 and 2 is dominated by the longitudinal component of γ zzzz , but for the molecule 3 and 4 the maximal tensor component is achieved for γ xxxx . The same conclusions can be drawn in relation to the components obtained for the calculation of the first hyperpolarizability. Domination of particular component indicates a substantial delocalization of charges in these directions. This electron distribution can be skewed by substituents, the enlarge of this redistribution is measured by dipole moment, and facility of redistribution in response to an externally applied electric field by hyperpolarizability.
From Fig. 9 we can see the direction of the electric dipole moment. It can be deduced also from Table 6 that for the molecules 1 and 2, the dipole moment vectors are directed mainly along the longest part of the molecule μ z while for molecules 3, 4, the dipole moment vectors in the direction of phosphine ligands μ x If we take into account the maximum values of γ zzzz for 1 and 2 and γ xxxx for 3, 4 a good agreement is obtained between theoretical and experimental results.
HOMO, LUMO and HOMO-LUMO-energy gaps have been also calculated in order to analyze the relationship of NLO properties with the molecular structure of the studied compounds. Interpretations of orbital energies give useful forecasting. As usually, the HOMO and LUMO energy levels depend on electron donating strength of donor and electron -withdrawing strength of acceptor, respectively.
The energy gap (∆E L−H = E LUMO − E HOMO ), explains the charge transfer interaction taking place within the ligands. The HOMO represents the ability to donate an electron and the LUMO represents the ability to obtain an electron. The HOMO and LUMO energies and HOMO-LUMO energy gaps are given in Table 6. The width of the energy gap obtained for investigated materials falls within limits 2-3 eV. Which correlates well with the maximum in the absorption spectrum, see Table 1. The reduction in the HOMO-LUMO energy gap explains eventually charge transfer interaction taking place within the molecules. Generally, if conjugation bonds in a molecule increases, the HOMO-LUMO gap decreases and leads to a bathochromic shift. The HOMO-LUMO (4) γ tot = 1 5 γ xxxx + γ yyyy + γ zzzz + 2 γ xxyy + γ xxzz + γ yyzz www.nature.com/scientificreports/ energy gap decreases also upon metal complexation (see Table 7) E LUMO -E HOMO for free ligand is higher than for complexes 1-4 what should be related to increasing of NLO properties. Based on the obtained experimental and theoretical results (see Supporting Information pages S10-S11) we can deduce that in our case the large second and third order optical nonlinearity is caused by strong intramolecular charge transfer between donors and acceptors through a conjugated transmitter.
The theoretical results show that the geometry of the molecule can determine nonlinear properties. The choice of the auxiliary ligands allows the direction of dipole moment of the complex to be modified and it can change the linear and nonlinear optical properties the whole system. Comparison of theoretical results with the values published in the literature indicates that all these complexes exhibit large microscopic and macroscopic second and third-order NLO properties.

Conclusion
In summary, we have reported herein the synthesis and full characterization of four specific organometallic complexes (1)(2)(3)(4). The UV-Visible absorption spectra as well as the cyclic voltammetry measurements indicated a different metal to ligand charge transfer (MLCT). Thus, the second and third-order nonlinear optical properties of these four organometallic complexes have been evaluated by means of second and third harmonic generation (SHG and THG) techniques. The values of the second order NLO susceptibility of our four complexes were found to be the highest for complex 4 while complex 1 showed the strongest third harmonic generation. The difference of obtained values of second and third nonlinear susceptibilities is due to modification of the energy states and the introduction of a charge transfer state upon complexation which are of different nature within the four metal complexes. Calculations correctly reproduce HOMO, LUMO energies and hyperpolarizabilities of the organometallic metal complexes 1-4. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecules. From theoretical calculation, it is clear that the presence of two Ph 3 P acting as the most electron-acceptor groups in 3 and 4 complexes skew the direction of the dipole moment causing electron delocalization in other direction than for the molecule 1 and 2. The possible modulation of the nonlinear optical susceptibility by the nature of the metal atom used and its coordination sphere is an important phenomenon which opens new perspectives for both photonic and opto-electronic applications.  www.nature.com/scientificreports/ Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/.