Far-Red to Near Infrared Emissive Aqueous Nanoparticles Based on a New Organic Material with Three BODIPY Dyes at the Periphery of the Core: A Combined Experimental and Theoretical Study

: A new organic material with three 4,4-difluoro-4-borata-3a-azonia-4a-aza- s -indacene dyes (BODIPYs) at the periphery of the central core is successfully synthesized (3BDP3T) and its corresponding aqueous nanoparticles are prepared via the encapsulation approach and characterized in detail both experimentally and theoretically with the aid of the Density Functional Theory (DFT). The linear and non-linear optical properties of the synthesized material are also studied. Until now, the development of organic materials with three BODIPYs as substituents is limited and their properties are not fully resolved. The obtained 3BDP3T-based nanoparticles exhibit far-red and near infrared (NIR) emission with photoluminescence quantum yields of 0.021, which is promising as a new fluorescent contrast agent in the far-red and NIR spectral regions.


Introduction
Acceptor-Donor-Acceptor (ADA) organic electronic materials are a class of functional dyes that provided the largest impact to the field of organic electronics and, especially, the small molecule-based organic photovoltaics (OPV) materials during the last five years [1][2][3][4][5]. According to this concept, an electron-donating conjugated oligomer is functionalized at its ends with two electron-deficient units among which dicyanovinylene groups are the most widely utilized [6]. Stronger heterocyclic acceptors were originally utilized less frequently despite their beneficial influence on the absorption properties, i.e., reducing the band gap and increasing the color tunability.
Such a heterocyclic electron withdrawing the building block is the 4,4-difluoro-4-borata-3a-azonia-4a-aza-s-indacene dye, which is more commonly known as BODIPY. BODIPYtype dyes are an emerging class of red/near infrared (NIR) emitters (and absorbers) [7,8] because, even though the monomeric BODIPY is a green-emitting fluorophore (quantum efficiency up to 100% with narrow absorption and emission bands < 50 nm) [9], it can be functionalized by means of a few synthetic steps so as to shift the energy gap into the NIR [10]. Discovered for the first time in 1968 by Treibs and Kreuz [11], BODIPYs are of wide importance and have a broad use as laser dyes in biological sensing, organic electronic, and other possible applications [12][13][14][15][16][17].
Taking these into account, we have recently reported the synthesis of a novel A-D-A type near infrared (NIR) organic material (referred to as NIRBDTE, for brevity, please see Figure 1 for the chemical structure) containing two BODIPY moieties as the (A) units and an oligothiophene segment as the electron donating (D) part [10]. NIRBDTE was then used as the emitter in NIR organic light emitting diodes (OLEDs) with the highest efficiency reported so far for a metal-free fluorescent material, emitting at 720 nm. Motivated by these results, we were interested in exploring alternative chemical approaches, such as going beyond the classical A-D-A type organic electronic materials, by functionalizing electron donating units with more than two BODIPY dyes for bioimaging. Organic materials with 3 BODIPYs meso substituted in the periphery of an electron donating molecule (D) are limited and their synthesis is particularly challenging. However, the development of stable meso substituted BODIPYs are the key synthetic intermediates toward higher dimensionality structures. These type of 2D or 3D organic materials are expected to provide new insights on the optical or electronic properties.
(D) are limited and their synthesis is particularly challenging. However, the devel of stable meso substituted BODIPYs are the key synthetic intermediates toward dimensionality structures. These type of 2D or 3D organic materials are expected vide new insights on the optical or electronic properties.
Fluorescent probes based on small organic molecules have become fund tools in the science of biology due to their ability to provide information about th zation and quantity of the biological molecules without having them to be gen modified [18]. One of the major disadvantages for the use of organic fluorophor oimaging is their failure to continuously fluoresce for extended periods. Moreov of fluorophores spectra are usually wide, which sometimes contributes to overla nals from numerous biological fluorophores. Therefore, between the different phores, BODIPYs are the most popular group. Their efficiency of the high photos sharp absorption and emission patterns, high fluorescence quantum yields, and tinction coefficients makes them perfect candidates for bioimaging [7,19].
Based on this, in this contribution, we present the successful synthesis and pr characterization of a new organic electronic material consisting of three BODIPY the periphery of the benzo[1,2-b:3,4-b′:5,6-b″]trithiophene (3BDP3T; Figure 1) for time. We manage to prepare 3BDP3T-based aqueous nanoparticles utilizing the e lation method and study its optical properties toward its application as far-red infrared (NIR) dye probe for fluorescent optical imaging. In order to shed some the experimental findings, a series of theoretical computations is also reported.  Fluorescent probes based on small organic molecules have become fundamental tools in the science of biology due to their ability to provide information about the localization and quantity of the biological molecules without having them to be genetically modified [18]. One of the major disadvantages for the use of organic fluorophores in bioimaging is their failure to continuously fluoresce for extended periods. Moreover, most of fluorophores spectra are usually wide, which sometimes contributes to overlap of signals from numerous biological fluorophores. Therefore, between the different fluorophores, BODIPYs are the most popular group. Their efficiency of the high photostability, sharp absorption and emission patterns, high fluorescence quantum yields, and high extinction coefficients makes them perfect candidates for bioimaging [7,19].
Based on this, in this contribution, we present the successful synthesis and properties characterization of a new organic electronic material consisting of three BODIPY dyes at the periphery of the benzo[1,2-b:3,4-b :5,6-b"]trithiophene (3BDP3T; Figure 1) for the first time. We manage to prepare 3BDP3T-based aqueous nanoparticles utilizing the encapsulation method and study its optical properties toward its application as far-red to near infrared (NIR) dye probe for fluorescent optical imaging. In order to shed some light on the experimental findings, a series of theoretical computations is also reported.

Instrumentation
Nuclear Magnetic Resonance (NMR): 1 H-NMR measurement was carried out in solution (1% w/v) using CDCl 3 (Acros 99.6%) as the solvent and tetramethylsilane (TMS) as the integral standard on a Varian 600 MHz NMR spectrometer (Palo Alto, California) at an ambient temperature.

Dynamic Light Scattering (DLS)
The structural study was performed using dynamic light scattering (DLS) in order to determine the mean diameter (d, nm) of nanodroplets and the polydispersity index (PdI) of the system. DLS measurements were performed using the Zetasizer NanoZS device (ZEN3600) from Malvern Instruments (Malvern, UK) equipped with He-Ne (632.8 nm) laser and detection was performed at a scattering angle of 173 • . The mean diameter of the dispersed nanodroplets was calculated by the Stokes-Einstein law.
where R H is the hydrodynamic radii of nanodroplets, k B is the Boltzmann constant, T is the absolute temperature, η viscosity of microemulsion (in specific temperature), and D is the diffusion constant, respectively [20]. After their preparation, the microemulsions were placed in a suitable glass cell in dustfree conditions. The experimental data were processed using version 6.32 of the Malvern Zetasizer Nano software (Malvern Panalytical Ltd., Enigma Business Park, Malvern, UK). The temperature during the measurements was constant at 25 • C. Experiments were performed in triplicate for each sample, and results were presented as an average of ± S.D.

Absorption and Photoluminescence
The absorption spectra of the tetrahydrofuran (THF) solutions and the aqueous Conjugated Polymer Nanoparticles (CPNs) were measured using a UV-Visible Analytik Jena AG Germany, Specord 205 spectrophotometer using a 1-cm path length quartz cuvette. The THF solutions were in dry conditions to prevent the stabilizers interference with the fluorescence measurement. The photoluminescence (PL) emission and the relative PL quantum yield (PLQY) was measured by PL spectroscopy when using a dilute fluorenone solution (excitation wavelength of 380 nm) in acetonitrile as the reference (Φr = 0.032) [21,22]. The used excitation wavelength was 520 nm. The cuvette was a 1 cm cuvette and 90 • . All the fluorescence measurements were performed under argon atmosphere. A software-controlled FS5 Spectrofluorometer (Edinburgh Instruments Ltd., Livingston, UK) enabled the acquisition of photoluminescence spectra. The photoluminescence quantum yield has been calculated from the equation below [23].
where, Φ X , is the photoluminescence quantum yield of the unknown sample, F, is the area of the integration of the emission intensities, n, is the refractive index of the sample and the reference, A, is the solution optical density at the excitation wavelength.
The indexes 'r' and 'x' are referred to as the refence and the unknown sample, respectively. Cyclic Voltammetry: The cyclic voltammetry was conducted on a VersaSTAT4 potentiostat galvanostat with platinum (Pt) disk, Pt wire, and standard calomel electrode (SCE) as the working electrode, counter electrode, and reference electrode, respectively, using a 0.1 M-solution of tetrabutylammonium hexafluorophosphate (n-Bu 4 NPF 6 ) in anhydrous acetonitrile at a potential scan rate of 50 mV s −1 . Thin films of samples were deposited onto the Pt disk working electrode from a chloroform solution. The potential of the SCE reference electrode was internally calibrated by using the ferrocene/ferrocenium redox couple (Fc/Fc + ). The electrochemical energy levels were estimated by the highest occupied molecular orbital E HOMO = −[4.8 + (E onse Ox − Fc 1/2 )] and lowest unoccupied molecular

Theoretical Calculations
We employed DFT to calculate a series of properties, the E HOMO and E LUMO , the first allowed electronic transition (excitation energy), the dipole moment, and the electronic (hyper)polarizabilities of 3BDP3Ta and 3BDP3Tb, both in the gas phase and in solution. In particular, E HOMO and E LUMO were calculated by employing a series of functionals (e.g., PBE1PBE/6-31G**, HSEH1PBE/6-311G** etc.) and their performance will be checked by using the experimental values. The computation of linear and non-linear optical response properties ((hyper)polarizabilities) will provide insights on the interaction of these derivatives with light, thus, revealing certain features associated with their structure-property relationship.
Linear and Non-Linear Optical Properties: Definitions. When a molecule is set in a uniform static electric field, F, its energy, E(F), is given by: where E 0 is the field-free energy, µ i , α ij , β ijk , and γ ijkl are the dipole moment, polarizability, first hyper-polarizability, and second hyper-polarizability components, respectively. A summation over repeated indices is implied. The polarizabilities and the hyper-polarizabilities are also called linear (L) and nonlinear optical (NLO) properties. The reported values for the dipole moment (µ), polarizability (α), and hyper-polarizabilities, first (β) and second (γ) are given by: Finite field approaches [24], by employing Equation (3), have been used to compute the (hyper)polarizability components, by applying a step field of 0.001 a.u.
The Density Functional Theory computations have been performed by using the GAUSSIAN 09 software [25]. The B3LYP/6-31G* method has been employed to calculate the molecular structures we have used in this work. Vibrational analysis was performed for all structures employed in this study to verify that a stationary point has been found in the potential energy surface.
Effect of the Environment on the L&NLO Properties: We have first computed the L&NLO properties in the gas phase. The solvent effect, on the properties of interest, has been calculated by employing the Polarizable Continuum Model, which uses the integral equation formalism variant [25]. This technique employs the solute cavity via a set of overlapping spheres. Many research groups contributed to its development (e.g., Tomasi, Barone) [26,27].
Nanoparticles Preparation: In more detail, 1 mg of 3BDP3T and 9 mg of poly(ethylene glycol) methyl ether-block-poly(lactide-co-glycolide) (mPEG-b-PLGA) were dissolved in 1 mL of THF. The choice of mPEG-b-PLGA was based on the fact that it is an FDA-approved and metabolizable copolymer [28]. The resulting solution is added to 7 mL of deionized water following a procedure described elsewhere [29]. The solution left overnight to allow complete evaporation of the THF and the volume of water lost was replaced. After this procedure, stable aqueous nanoparticles containing the 3BDP3T are formed. The hydrophobic PLGA segments are liable to entangle with 3BDP3T and the hydrophilic polyethylene glycol (PEG) chains should extend into the aqueous phase. The obtained nanoparticles were then filtered through a 0.2-µm cellulose acetate filter. To evaluate the sizes of the formatted aqueous nanoparticles, dynamic light scattering (DLS) measurements were performed at room temperature of 25 • C a day after their preparation.

Synthesis and Properties Characterization
With a view for establishing general protocols for (organic) semiconductors design, we consider that BODIPY might be an ideal acceptor end-unit because it has strong electronwithdrawing characteristics, and it is expected to provide both negative inductive (−I) effects originating from "through-bond" polarizations [10], and mesomeric (−M) effects [30], originating from π-bond polarizations. Such an approach is expected to facilitate both delocalization and stabilization of charge carriers (e.g., electrons). In practice, the development of BODIPY-based organic semiconductors and, especially those that contain more than two BODIPY units, has, so far, lagged behind that of other π-deficient units, mainly because of stability issues during the synthesis. However, thanks to a recently developed synthetic protocol, stable α,β-unsubstituted BODIPYs functionalized solely on the meso position can be successfully produced and integrated into more complex structures [10]. Following this approach, we performed a Stille cross-coupling reaction between the 10-(5bromothiophen-2-yl)-5,5-difluoro-5H-4λ 4 ,5λ 4 3,2]diazaborinine and the 2,5,8-tris(trimethylstannyl)benzo[1,2-b:3,4-b :5,6-b"]trithiophene to obtain the 3BDP3T (Scheme 1) that contains three BODIPY dyes at the terminal of the benzo[1,2-b:3,4-b :5,6-b"] trithiophene core.
1 H-NMR analysis revealed the successful synthesis of the small molecule dyes. The BODIPY's protons (6H) were clearly observed with independent peaks at 6.65, 7.42, 7.58, and 7.98 ppm while the ratio of the integrated area between the BODIPY's and thiophenes' protons (7.24 ppm) was 2, confirming the expected structure. The UV-Visible absorption and photoluminescence spectra of 3BDP3T were recorded in tetrahydrofuran (THF) solution.
1 H-NMR analysis revealed the successful synthesis of the small molecule dy BODIPY's protons (6H) were clearly observed with independent peaks at 6.65, 7. and 7.98 ppm while the ratio of the integrated area between the BODIPY's and thio protons (7.24 ppm) was 2, confirming the expected structure. The UV-Visible abs and photoluminescence spectra of 3BDP3T were recorded in tetrahydrofuran (TH tion. Figure 2a shows an intense absorption peak with λmax at 520 nm (logε = 5.28) emission spectrum with λmax at 630 nm and a shoulder at 680 nm. The photolumin quantum yield (PLQY) found 0.029 ± 0.011 from three independent measuremen large stoke shift ((c. 3300 cm −1 ), which is considerably higher than for "normal" BO (c. 300 cm −1 )) that is shown in 3BDP3T is desirable because we can shift the emissio tra more to the near infrared region (>650 nm). Especially, the range of 1000-1 (short wave infrared, SWIR) is particularly useful for bioimaging, as this electrom field does not interfere with the absorption and emission of radiation due to the tion of various biological fluids, while it is less harmful to tissues and absorption ra at long wavelengths [31].
Cyclic voltammetry was performed to estimate the energy levels of 3BDP3T. idation and reduction potentials of 3BDP3T are shown in Figure 2b. 3BDP3T exh versible reduction peaks and irreversible oxidation peaks with oxidation and re onset potentials at 1.44 V vs. a standard calomel electrode (SCE) and −0.5 V vs. S spectively, resulting in EHOMO and ELUMO values of −6.14 eV and −3.91 eV, respectiv Scheme 1. Synthetic route towards the preparation of 3BDP3T. Figure 2a shows an intense absorption peak with λ max at 520 nm (logε = 5.28) and an emission spectrum with λ max at 630 nm and a shoulder at 680 nm. The photoluminescence quantum yield (PLQY) found 0.029 ± 0.011 from three independent measurements. This large stoke shift ((c. 3300 cm −1 ), which is considerably higher than for "normal" BODIPYs (c. 300 cm −1 )) that is shown in 3BDP3T is desirable because we can shift the emission spectra more to the near infrared region (>650 nm). Especially, the range of 1000-1700 nm (short wave infrared, SWIR) is particularly useful for bioimaging, as this electromagnetic field does not interfere with the absorption and emission of radiation due to the absorption of various biological fluids, while it is less harmful to tissues and absorption radiation at long wavelengths [31].
Cyclic voltammetry was performed to estimate the energy levels of 3BDP3T. The oxidation and reduction potentials of 3BDP3T are shown in Figure 2b. 3BDP3T exhibits reversible reduction peaks and irreversible oxidation peaks with oxidation and reduction onset potentials at 1.44 V vs. a standard calomel electrode (SCE) and −0.5 V vs. SCE, respectively, resulting in E HOMO and E LUMO values of −6.14 eV and −3.91 eV, respectively.

Theoretical Calculations
The reported computational results will focus on: (a) the rationalization of absorption energy by employing Natural Transition Orbital analysis (NTO) [32] EHOMO and ELUMO, and the first electronic excitation energy, (c) the linear and no optical properties (L&NLO) by computing the static (hyper)polarizabilities of 3 and 3BDP3Tb (Figure 3), (d) the effect of the solvent and small structural change optical and non-linear optical properties of interest will also be discussed, and (e fect of BODIPY, as an electron acceptor, on the L&NLO properties, will be discus compared with other well-known strong electron acceptors (NO2, CN). Electron a defines those atoms or groups that withdraw electron density [33].
Computation of EΗOMO and ΕLUMO of 3BDP3Ta. In Table 1, we present the EΗ ΕLUMO of derivative 3BDP3Ta, computed by a series of functionals and basis set these results, it is inferred that: (a) the best EΗOMO is given by PBE1PBE/6-31G**, B3P 311G**, (b) the best ΕLUMO is given by HSEH1PBE/6-311G**, B3PW91/6-311G**, (c B3LYP, B3LYP functionals overestimate the HOMO-LUMO gap, compared with periment. A similar trend is observed for the value computed with the MP2 Therefore, it is inferred that, of all considered functionals, B3PW91/6-311G** has ently, the best performance when compared with the available experimental data EΗOMO and ΕLUMO. With regard to the EΗOMO-ΕLUMO gap, the value which has the agreement with the experiment is given by the HSEH1PBE/6-311G** method.

Theoretical Calculations
The reported computational results will focus on: (a) the rationalization of the first absorption energy by employing Natural Transition Orbital analysis (NTO) [32], (b) the E HOMO and E LUMO , and the first electronic excitation energy, (c) the linear and non-linear optical properties (L&NLO) by computing the static (hyper)polarizabilities of 3BDP3Ta and 3BDP3Tb (Figure 3), (d) the effect of the solvent and small structural changes on the optical and non-linear optical properties of interest will also be discussed, and (e) the effect of BODIPY, as an electron acceptor, on the L&NLO properties, will be discussed and compared with other well-known strong electron acceptors (NO 2 , CN). Electron acceptor defines those atoms or groups that withdraw electron density [33].    Computation of E HOMO and E LUMO of 3BDP3Ta. In Table 1, we present the E HOMO and E LUMO of derivative 3BDP3Ta, computed by a series of functionals and basis sets. From these results, it is inferred that: (a) the best E HOMO is given by PBE1PBE/6-31G**, B3PW91/6-311G**, (b) the best E LUMO is given by HSEH1PBE/6-311G**, B3PW91/6-311G**, (c) CAM-B3LYP, B3LYP functionals overestimate the HOMO-LUMO gap, compared with the experiment. A similar trend is observed for the value computed with the MP2 method. Therefore, it is inferred that, of all considered functionals, B3PW91/6-311G** has, apparently, the best performance when compared with the available experimental data for both E HOMO and E LUMO . With regard to the E HOMO -E LUMO gap, the value which has the closest agreement with the experiment is given by the HSEH1PBE/6-311G** method. Rationalization of the Observed First Electronic Absorption. The leading NTOs, describing the first allowed electronic transition of 3BDP3Ta, have been computed by two methods (Figure 4). Employing the CAM-B3LYP/6-31G** method, we find that two pairs of NTOs, with weights of 0.70 and 0.19, are required to describe the first electronic transition. This involves mainly one BODIPY unit (Figure 4). Using the HSEH1PBE/6-311G** approach, we also find two NTOs, with weights of 0.77 and 0.22. However, the transition involves two BODIPY units and the intervening thiophene groups. It appears that a charge transfer (CT) takes place from the thiophene groups to the BODIPY units. It is observed that the two methods (CAM-B3LYP/6-31G**, HSEH1PBE/6-311G**) give a rather different picture for the transition. It has been noted that CAM-B3LYP overestimates |E HOMO − E LUMO |. This may be due to the fact that the present intra-molecular CT transition (Figure 4) is rather short [34].
Computation of the (hyper)polarizabilities. The CAM-B3LYP/6-31G* method has been employed to compute the dipole moment and the (hyper)polarizabilities of derivatives 3BDP3Ta and 3BDP3Tb, both in the gas phase and in solution (solvent: chloroform, water). This method has been successfully applied for the computation of NLO properties of organic and inorganic derivatives [35,36]. The results are presented in Table 2.
Solvent effect. It is observed that the solvent has a significant effect on all the properties. The hyperpolarizabilities β and γ are those which are most affected by the solvent. Thus, it is observed: β(sol)/β(gas) = 1.8 and γ(sol)/γ(gas) = 1.94, where β(sol) and γ(sol) denote the hyperpolarizability values in solution and β(gas) and γ(gas) are the corresponding values in the gas phase. A small variation of the basis set (6-31G** and 6-311G**) led to insignificant changes of the L&NLO properties.
In order to study the effect of the solvent polarity, we report computations in the presence of a high polar solvent (water, ε = 80) since the nanoparticles will be formed in water. The results are shown in Table 2. It is observed that, although the solvent's polarity is substantially increased (c.a 94%), the optical and electrical response properties of both molecules are slightly affected. For example, it is seen that, for the optical response properties of 3BDP3Ta, α(wat) = 1.1 α(chloroform), β(wat) = 1.2 β(chloroform), where α, β, denote the average pol/ty and first hyperpolarizability (CAM-B3LYP/6-311G**), respectively. As far as concerns about the optical absorption of 3BDP3Ta, λ(wat) is slightly red shifted, compared with that computed within chloroform. Similar trends are observed for the 3BDP3Tb derivative.  Table 2. The dipole moment (a.u.), (hyper)polarizabilities (a.u), the excitation energy (Eexc, eV), the absorption wavelength (λ, nm) of the first electronic allowed transition and the total energy (Hartrees). All the properties were computed at the gas phase optimized geometry (B3LYP/6-31G**).   In terms of a comparison of the properties, p = α xx , β xxx , and γ xxxx , computed with the CAM-B3LYP/6-311G* method with those calculated with the MP2/6-311G* technique shows the adequacy of the former for the computation of L&NLO optical properties of the 3BDP3Ta/b derivatives. It is observed that, for 3BDP3Ta, the ratio: p(MP2)/p(CAMB3LYP) = 0.99, 0.89, and 0.79, for the polarizability, first and second hyperpolarizability component, respectively. By employing the HSEH1PBE functional, the ratio p(MP2)/p(HSEH1PBE) takes the values of 0.89, 0.37, and 0.24 for α xx , β xxx , and γ xxxx , respectively.

Molecule
We have also computed the properties of two configurations of 3BDP3T (Figure 3). The first (3BDP3Ta) has the sulfur atoms of thiophenes in a cis arrangement (3BDP3Ta) and the second (3BDP3Tb) in trans. In derivative 3BDP3Tb, the conformation, where the sulfur atoms of thiophenes, are in a trans position that lies lower (2.6 kcal/mol) than the corresponding conformation, where the sulfur atoms of thiophenes are in a cis position (3BDP3Tb). This structural change has a very significant effect on the dipole moment (µ) and the first hyperpolarizability (β). µ(cis)/µ(trans) = 15.6 and β(cis)/β(trans) = 7.2 (9) This finding highlights the importance of these properties as probes of small differences in the molecular structure. A modest effect is observed for the polarizability and the second hyperpolarizability, while both isomers have practically the same E exc .
In order to further explain, qualitatively, the noticeable difference on β, due to cis and trans arrangement of thiophenes (3BDP3Ta,3BDP3Tb), the density of the first hyperpolarizability, β, has been computed. This property has been successfully used to explain NLO property differences, resulting by structural changes [35,36]. Only the diagonal component, β xxx , of the density ( Figure 5) is reported and analyzed, since it was found that the electronic β xxx value is affected more upon the conformational change (Figure 3), that is ∆β xxx (3BDP3Ta−3BDP3Tb) = 37,891 a.u. (CAMB3LYP/6-31G**). Therefore, the β xxx density differences are expected to reveal the origin of the noticeable alteration of the β value, upon the conformational change. The computed densities for 3BDP3Ta, 3BDP3Tb are depicted in Figure 5. The Multiwfn software was used.
Electron. Mater. 2021, 2, FOR PEER REVIEW 11 upon the conformational change. The computed densities for 3BDP3Ta, 3BDP3Tb are depicted in Figure 5. The Multiwfn software was used. It is observed that, for 3BDP3Ta (Figures 3 and 5), the positive contribution exceeds the corresponding negative one, resulting in a positive βxxx value (15,800 a.u.). Upon changing the positions of thiophenes (cis-trans), the negative contribution to βxxx density is increased, especially in the periphery of the core, thus, changing the sign of the βxxx value (−22,011 a.u.).
Comparison of BODIPY with NO2 and CN. The effect of BODIPY, as an electron acceptor, on the L&NLO properties has been checked by comparing the performance of BOD-IPY with that of NO2 and CN, which are known to be very efficient electron acceptors ( Figure 6) [33]. It is observed that, for 3BDP3Ta ( Figures 3 and 5), the positive contribution exceeds the corresponding negative one, resulting in a positive β xxx value (15,800 a.u.). Upon changing the positions of thiophenes (cis-trans), the negative contribution to β xxx density is increased, especially in the periphery of the core, thus, changing the sign of the β xxx value (−22,011 a.u.).
Comparison of BODIPY with NO 2 and CN. The effect of BODIPY, as an electron acceptor, on the L&NLO properties has been checked by comparing the performance of BODIPY with that of NO 2 and CN, which are known to be very efficient electron acceptors ( Figure 6) [33].
It is observed that, for 3BDP3Ta (Figures 3 and 5), the positive contribution the corresponding negative one, resulting in a positive βxxx value (15,800 a.u. changing the positions of thiophenes (cis-trans), the negative contribution to βxxx is increased, especially in the periphery of the core, thus, changing the sign of value (−22,011 a.u.).
Comparison of BODIPY with NO2 and CN. The effect of BODIPY, as an electro tor, on the L&NLO properties has been checked by comparing the performance IPY with that of NO2 and CN, which are known to be very efficient electron a ( Figure 6) [33]. The results of Table 3 show that µ(CN) > µ(NO2) > µ(BODIPY), but P(BO P(NO2) > P(CN), where p = α, β, or γ. In fact, BODIPY as an electron acceptor, le much larger α, β, or γ in comparison with NO2 or CN. This is a very useful findin large NLO properties and their tuning are required for many applications (e.g., o tronic technologies, optical switching, and telecommunications) [37,38]. The results of Table 3 show that µ(CN) > µ(NO 2 ) > µ(BODIPY), but P(BODIPY) > P(NO 2 ) > P(CN), where p = α, β, or γ. In fact, BODIPY as an electron acceptor, leads to a much larger α, β, or γ in comparison with NO 2 or CN. This is a very useful finding, since large NLO properties and their tuning are required for many applications (e.g., optoelectronic technologies, optical switching, and telecommunications) [37,38]. Table 3. The dipole moment (a.u.) (hyper)polarizabilities (a.u), the energy of the HOMO and LUMO, E HOMO and E LUMO , respectively the E HOMO − E LUMO gap the excitation energy (E exc ; eV) the absorption wavelength (λ; nm) of the first electronic allowed transition of 1a with a series of acceptor groups (A). All values are given in a.u. It is also observed that the type of the acceptor tunes the |H − L| (=|E HOMO − E LUMO |) and transition energy, E exc . It was found that |H − L|(CN)> |H − L|(NO 2 ) >|H − L| (BODIPY) and E exc (CN) > E exc (NO 2 ) > E exc (BODIPY). The latter agrees with the observed alteration of the absorption wavelength, λ, of the three acceptors. For example, λ is 569 and 400 nm for BODIPY and CN, respectively.

Preparation of Nanoparticles
In this work, we prepared 3BDP3T nanoparticles with the encapsulation method. From the three independent DLS measurements, the aqueous nanoparticles show to exhibit a unimodal size distribution with a hydrodynamic diameter of 123.53 ± 0.38 nm (Figure 7), which reflect the reproducibility of the hydrodynamic diameter and the FWHM of the nanoparticle's distribution. Simultaneously with the DLS measurements, the zeta potential of the nanoparticles was measured. The prepared aqueous nanoparticles exhibit a substan-tial and negative zeta potential of −8.99mV, which is higher than −25 mV. It is well-known that colloidal systems with a zeta potential value of −25 mV or lower (i.e., more negative) exhibit a long-term colloidal stability [39]. The origin of a negative zeta potential has been addressed in previous studies [40] and it is attributed to oxidative defects on the surface of the nanoparticles or to the presence of the π-polarizations of the organic material rings that enable stronger attractive Van der Waals forces and hydrophobic interactions. Therefore, when the organic material is encapsulated inside the amphiphilic copolymer, those interactions are minimized, resulting in lower zeta potential values. has been addressed in previous studies [40] and it is attributed to oxidative defects on the surface of the nanoparticles or to the presence of the π-polarizations of the organic material rings that enable stronger attractive Van der Waals forces and hydrophobic interactions. Therefore, when the organic material is encapsulated inside the amphiphilic copolymer, those interactions are minimized, resulting in lower zeta potential values.     While the absorption maximum of 3BDP3T-based nanoparticles is slightly blueshifted by 5 nm versus the corresponding 3BDP3T in the THF solution. The PL maximum peaks are significantly red-shifted by 12 nm and 72 nm, respectively. The aqueous 3BDP3T nanoparticles display PL at the far-red and NIR with a PLQY of 0.021 ± 0.003, which is slightly reduced versus the PLQY of the 3BDP3T in the THF solution, showing that this fabrication methodology for the specific 3BDP3T maintains the PLQY unaltered.

Conclusions
In this work, the successful synthesis and properties characterization of a new organic electronic material consisting of three BODIPY dyes at the periphery of the While the absorption maximum of 3BDP3T-based nanoparticles is slightly blue-shifted by 5 nm versus the corresponding 3BDP3T in the THF solution. The PL maximum peaks are significantly red-shifted by 12 nm and 72 nm, respectively. The aqueous 3BDP3T nanoparticles display PL at the far-red and NIR with a PLQY of 0.021 ± 0.003, which is slightly reduced versus the PLQY of the 3BDP3T in the THF solution, showing that this fabrication methodology for the specific 3BDP3T maintains the PLQY unaltered.

Conclusions
In this work, the successful synthesis and properties characterization of a new organic electronic material consisting of three BODIPY dyes at the periphery of the benzo[1,2-b:3,4b :5,6-b"]trithiophene (3BDP3T) is presented for the first time. Until now, the development of organic materials with three BODIPYs as substituents is limited and their properties are not fully resolved. We manage to prepare 3BDP3T-based aqueous nanoparticles by utilizing the encapsulation method and study its optical properties toward its application as far-red to near infrared (NIR) dye probe for fluorescent optical imaging. The aqueous 3BDP3T nanoparticles display PL at the far-red and NIR with a PLQY of 0.021 ± 0.003, which is slightly reduced versus the PLQY of the 3BDP3T in the THF solution, showing that this fabrication methodology for the specific 3BDP3T maintains the PLQY unaltered. From the theoretical study, the main points emerging are the following. The best E HOMO has been computed by PBE1PBE/6-31G**and B3PW91/6-311G**. The best E LUMO has been calculated by HSEH1PBE/6-311G** and B3PW91/6-311G**. The CAM-B3LYP and B3LYP functionals as well as the MP2 method overestimate the E HOMO − E LUMO gap. The best E HOMO − E LUMO gap has been computed by HSEH1PBE/6-311G**. The CAM-B3LYP/6-31G** method provided satisfactory L&NLO properties, as a comparison with the MP2 method has shown. In derivative 3BDP3Tb, the conformation, where the sulfur atoms of thiophenes are in a trans position, lies lower (2.6 kcal/mol) than the corresponding conformation, where the sulfur atoms of thiophenes are in a cis position (3BDP3Tb). This structural change imposes noticeable alterations to µ and β, in contrast to α, γ, and E exc , where the effect of the structure is of less importance. The effect of the structure to β was further investigated by analyzing the first hyper-polatizanity density [41]. We have employed two methods to rationalize the observed first absorption of 3BDP3Ta. Both methods give two pairs of NTOs for the description of the first electronic transition. The HSEH1PBE/6-311G** method predicts a transition that involves two BODIPY units and the intervening thiophene groups. Comparison of the BODIPY electron acceptor with other known groups revealed its significant efficiency in tuning the L&NLO response properties of 3BDP3T.