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Article

π-Extended Boron Difluoride [NՈNBF2] Complex, Crystal Structure, Liquid NMR, Spectral, XRD/HSA Interactions: A DFT and TD-DFT Study

by
Abdulrahman A. Alsimaree
1,*,
Nawaf. I. Alsenani
2,
Omar Mutlaq Alatawi
3,4,
Abeer A. AlObaid
5,
Julian Gary Knight
3,
Mouslim Messali
6,
Abdelkader Zarrouk
7 and
Ismail Warad
8,*
1
Department of Basic Science (Chemistry), College of Science and Humanities, Shaqra University, Afif, P.O. Box 33, Shaqra 11961, Saudi Arabia
2
Department of Chemistry, Faculty of science, University of Albaha, Alagig 65779-7738, Saudi Arabia
3
Department of Chemistry, School of Natural and Environmental Sciences, Newcastle University, Newcastle Upon Tyne NE1 7RU, UK
4
Department of Chemistry, Faculty of science, University of Tabuk, Tabuk 47512, Saudi Arabia
5
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
6
Laboratory of Applied and Environmental Chemistry (LCAE), Mohammed First University, Oujda 60000, Morocco
7
Laboratory of Materials, Nanotechnology, and Environment, Faculty of Sciences, Mohammed V University in Rabat, Agdal-Rabat P.O. Box. 1014, Morocco
8
Department of Chemistry and Earth Sciences, Qatar University, Doha P.O. Box 2713, Qatar
*
Authors to whom correspondence should be addressed.
Crystals 2021, 11(6), 606; https://doi.org/10.3390/cryst11060606
Submission received: 21 April 2021 / Revised: 16 May 2021 / Accepted: 23 May 2021 / Published: 27 May 2021
(This article belongs to the Special Issue New Trends in Crystals at Saudi Arabia)
Browse Figures
Review Reports Versions Notes

Abstract

:
The novel tetrahedral 10-(4-carboxyphenyl)-2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl-5H-di-pyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinin-4-ium-5-uide [NՈNBF2] BODIPY complex was prepared in a very good yield and via one-pot synthesis. The desired [NՈNBF2] has been used as a model complex for XRD/HSA interactions and DFT/B3LYP/6-311G(d,p) computations. The tetrahedral geometry around the boron center was demonstrated by DFT optimization and XRD-crystallography. The 1H, 11B, and 19F-NMR spectra were used also to support the high symmetrical BODIPY via π-extended phenomena. Moreover, the values of the DFT-calculated structural bond lengths/angles and DFT-IR were matched to the corresponding experimental XRD and IR parameters, respectively. The crystal lattice interactions were correlated to Hirshfeld surface analysis (HSA) calculations. Calculations of the Mulliken Atomic Charge (MAC), Natural Population Analysis (NPA), Global reactivity descriptors (GRD), and Molecular Electrostatic Potential (MEP) quantum parameters were performed to support the XRD/HSA interactions result. Analysis of the predicted Density of States (DOS), molecular orbital, and time-dependent density functional theory (TD-DFT) calculations have been combined to explain the experimental UV-vis spectra and electron transfer behavior in [NՈNBF2] complex using MeOH and other four solvents.

Graphical Abstract

1. Introduction

Complexes of boron with dipyrromethene ligands (BODIPY) as a class of organic complexes are currently of high interest due to their uses in several dye applications such as fluorescent switches, biomolecule markers, organic solar cells, chemosensors, laser dyes, photodynamic therapy, and fluorescence surface labeling [1,2,3,4,5]. Moreover, there has been a rapid growth of new preparation strategies for the functionalization of B-complexes to enable binding to a biological target in order to change its optical properties; these strategies include cross-coupling reaction, halogenation, and nucleophilic aromatic substitution on the dipyrromethene part [6,7,8]. The big challenges in the chemistry of BODIPY are in developing compounds with enhanced emission and absorption profiles and the discovery of dyes with new properties [9,10,11].
The ongoing accommodation is explicit from the considerable number of articles being reported about the synthesis and characterization of BODIPY boron complexes as well as their varied applications such as biological labels, tunable laser dyes, probes, photoactive, photovoltaic devices, fluorescent nanocars, light-emitting devices, photoactivatable compounds, energy transfer, triplet photosensitizers, PDT, photocatalytic reactions, triplet–triplet annihilation up-conversion, and photo-induced production [12,13,14,15,16,17,18,19,20,21,22,23,24,25,26]. Moreover, various BODIPY dyes are commercially available as probes for bio-imaging, biological labels, and laser dyes [27,28]. Recently, the same complex and its analogs were prepared by Shipalova et al.; the author’s studies focused on the pH and polarity fluorescent molecular sensorics involving the BODIPY ligand. Moreover, none of the complexes structures were solved by XRD crystal nor was the π-extended boron difluoride phenomena studied [28].
There are a considerable number of papers concerning the BODIPY difluoride complexes, but few of them have been supported by X-raying a single crystal; therefore, herein, we have synthesized new [NՈNBF2] and characterized the structure by XRD. The solution-phase NMR and UV-Vis. spectra helped in supporting the π-extended boron difluoride phenomena in the [NՈNBF2] complex. The interactions in the structure have been confirmed by XRD/HSA analysis; moreover, the DFT/XRD structural parameters were successfully matched. The results of TD-DFT calculations, including methanol solvation, agreed well with the experimental UV-Vis behavior of the [NՈNBF2] complex.

2. Experimental

2.1. Computational

The HSA was carried out through the CIF file data and using the Crystal Explorer 3.1 program (version 17, University of Western Australia, Perth, Australia) [29]. All the DFT calculations were performed in gaseous phase at the DFT/B3LYP/6-311G(d,p) level of theory via Gaussian09 software (version 09, Gaussian Inc., Wallingford, CT, USA) [30].

2.2. Materials and Synthesis

Commercially available materials and solvents used in this study were purchased from commercial suppliers (Sigma Aldrich, Fluorochem and Alfa Aesar). The desired π-extended boron difluoride [NՈNBF2] complex has been prepared according to the published procedure [30]. The NMR was performed on a JEOL ECS 400 MHz Bruker Advance 300 (Bruker GmbH, Berlin, Germany) instrument using CDCl3 as solvent at RT. First, 10 mg of the complex powder was suspended in 3 ml of CDCl3, the clean solution was decanted to 3mm Wilmad NMR tube and filled up to ≈3 cm length to be used for the H, B, and F NMR. Since NMR showed that the elements H, B, and F have high natural abundance <99%; therefore, classical NMR was performed with 90° pulse and 8 to 32 scans and TMS reference for 1H-NMR, CFCl3 reference for 19F-NMR and BF3.OEt2 for 11B-NMR were used with UV-Vis on a TU-1901 double-beam UV-Vis spectrophotometer (PerkinElmer Inc., Waltham, MA, USA).

2.3. XRD-Structure

The single crystal X-ray data of the complex were collected on a Bruker D8 Quest diffractometer (Bruker GmbH, Berlin, Germany) (Mo-Kα radiation λ = 0.71073 Ǻ). The structure was solved by direct methods using SHELXS and SHELXTL packages (Uni. Gottingen, Gottingen, Germany), which were refined using full-matrix least squares procedures on F2 via the program SHELXL [31,32]. All hydrogen atoms were included at calculated positions using a-riding model with C–H distances of 0.93 Å for sp2 carbons and 0.96–0.97 Å for sp3 carbons. The isotropic displacement parameters were Uiso(H) = 1.2Ueq(C) for methylene groups and sp2 carbons and Uiso(H) = 1.5Ueq(C) for methyl groups. The crystal data and refinement details are given in Table 1.

3. Results and Discussion

3.1. Preparation and NMR

The desired [NՈNBF2] complex was synthesized according to the reported method [30] as shown in Scheme 1. The negative charge of the dipyrromethene ligand can be fully delocalized across the extended π-system, and this is expected to result in a symmetrical electron distribution between N1 and N2 which are bridged by the boron center, as shown in Scheme 1.
The experimental solution-phase 1H, 11B and 19F-{1H }-NMR spectra in CDCl3 support the effective conjugation of organic π-bonds in the BODIPY in system to form a highly symmetrical hybrid structure (Scheme 1 and Figure 1). The δv-symmetry reduces the number of protons environment to 6 instead of 12; all the protons groups chemical shifts are identified directly and labeled in the spectrum in Figure 1a. Moreover, as expected, the 11B-{1H }-NMR spectrum displays a triplet (128 Mhz, δ = 1.0 ppm), as seen in Figure 1b due to coupling to two equivalent fluorine atoms, and the 19F-{1H}-NMR shows at 1:1:1:1 quartet (376.5 MHz, δ = −146.3 ppm), resulting from two equivalent fluorine atoms due the π-extended behavior coupled to the boron [33,34]. NMRDB [35] and GIAO-DFT/B3LYP/6-311G(d,p) NMR [30] were performed using same references and CDCl3 solvent, and the results are inserted into Figure 1 together with their experimental relatives. The difference in the theoretical calculations is not surprising, because in theory, NMR cannot determine the π-extended phenomena; therefore, the BODIPY in the [NՈNBF2] complex becomes an asymmetrical ligand and has no-C2-plane of symmetry that can be seen from the proton chemical shifts in Figure 1a,b. The NMRDB 1H-NMR chemical shifts and splitting together with the Exp. NMR are in good agreement. The only difference is that the NMRDB-1H-NMR perceived protons of 3 and of 4 groups as being identical and having the same chemical shift. Meanwhile, in 11B-NMR (Figure 1d) and 19F (Figure 1f), the DFT neglected the effect of the two nuclei on each other; therefore, no splitting was detected, resulting in a simple system: singlet for B atoms and doublet for F atoms.

3.2. XRD and DFT

The formation of the desired boron complex was confirmed via XRD analysis, as shown below. Analysis and comparison between the experimentally determined XRD and the computed DFT/B3LYP/6-311G(d,p)-optimized structures and their structural parameters is discussed below.
The B-complex was crystalized in a Triclinic/P-1 system; the molecular structures along with angles and bond lengths are illustrated in Figure 2a and Table 2. Figure 2a and Table 2 indicate the expected tetrahedral geometry of the boron center with N,N-chelation and 2F ligands [N-B-N angle (107.2°) F-B-F angle (109.5°)]. Formally, the boron center is coordinated to one of the N atoms via an ionic bond and to the other via a coordination covalent bond to form a slightly strained-six membered ring that is perpendicular to the plane of the F-B-F group. The 2B-N (1.543 Å), B-F1 (1.397 Å), and B-F2 (1.389 Å) bond lengths are consistent with the reported data for similar tetra-coordinate boron systems [32,33,34,35,36,37,38]. The DFT theoretical calculations demonstrated a high degree of congruence, as seen in Figure 2b. Quantification of the level of agreement between the theoretical and experimental bonds lengths and angles is shown in Table 2.
The XRD experimental data are in excellent agreement with the results of DFT calculations; as seen in Figure 3, the bond lengths in both DFT and XRD reflected a very good agreement (Figure 3a), with a 0.954 correlation coefficient (Figure 3b). Similarly, DFT/XRD angles reflected a higher degree of compatibility compared to the bond lengths (Figure 3c) with a 0.971 correlation coefficient (Figure 3d). DFT/XRD dihedral angles should reflect a higher degree of compatibility compared to the angles (Figure 3e) with a 0.980 correlation coefficient (Figure 3f). Figure 3 reflected a high congruence between XRD and DFT analysis: ≈95% in the case of bonds, ≈97% in the case of angles, and ≈98% in the case of dihedral angles. The slight difference in the bonds, the angles, and dihedral angles can be attributed to the dynamic changes in bonds lengths and the angle values due to the difference in the phases. As in the DFT, the freedom to elongate the bonds and change the angle values is much greater in the gas state compared to the XRD solid state. Moreover, the absence of the internal molecular forces between the molecules in DFT may give both the angles and the bonds greater space and dynamic freedom compared to the XRD packed solid-state, which is with various intermolecular forces, resulting in a rigid lattice.

3.3. XRD Packing and HSA Investigation

In the packing mode of the desired B-complex crystal, a “tail-to-tail” dimer interaction was detected via X-ray and computed by HSA for the first time, as seen in Figure 4. For each molecule tail, two short hydrogen bonds of type O-H….O=C with 1.788 and 1.870 Å formed a very stable 2D-S8 synthon dimer (Figure 4a). Two types of CMe-H…..F-B H-bonds with 2.658 Å formed 2D-S12 synthon, as seen in Figure 4b; there were another four CringH….O=C H-bonds: two with 2.659 Å that formed 1D supramolecular extensions and two with 2.699 Å that formed 2D-S10 synthon, as seen in Figure 4c. No C-H...π or π–π stacking connections were detected in the complex lattice.
To understand the molecule mode surface interactions with the surrounding molecules [36,37,38,39,40,41,42,43,44,45,46,47], HSA computation was carried out in the 0.89 to 1.98 a.u. range, as shown in Figure 5. The dnorm reflected the presence of two large red spots that are consistent with H….O hydrogen bonds types only; the H….F hydrogen bond detected by XRD was not found by HSA (Figure 5a). No C-H...π or π–π stacking connections were detected in the shape index, as seen in Figure 5b. Accordingly, the results of HSA supported well the XRD-packing outcome. Furthermore, the inside Hatom…Allatom outside two diminution-fingerprint plots contact ratios are illustrated in Figure 5c. The H…H interactions were found to have the highest contributions (70.6%); meanwhile, the H….B was found to have the lowest contributions, and the other H…X interactions were illustrated in [H…C>H…F>H…O>H…N] order.

3.4. MEP, Charges, and GRD Investigations

The MEP, MAC, and NPA calculation reflected the presence of nucleophilic/electrophilic centers at the surface, as shown in Figure 6. For example, the MEP, showed the O and F atoms as nucleophilic centers with the red color; meanwhile, the blue color labeled the H of carboxylic acid as very strong electrophile sites, and a couple of Hs belong to Me and Ph as electrophilic centers; the positive and negative charges at H and O in the carboxylic part supported the tail-to-tail hydrogen bonds interactions, as seen in Figure 6a. NPA and MAC charge population charges showed O and F atoms with negative charge (Figure 6b and Table 3). Moreover, the B and all hydrogen atoms are with positive charge, and the H4, which is the H of the carboxylic group, possessed the highest positive charge 0.265e MAC and 0.468e for NPA (Table 3). A good correlation coefficient between NPA/MAC charges plotted with a 0.9041 value has been observed, as seen in Figure 6c. The MPE, NPA, and MAC results are in a high degree of correlation with the HSA computed as well as the XRD packing.
The GRD quantum parameters such as chemical potential (μ), the Electrophilicity (ω), Hardness (ƞ), Softness (σ), and Electronegativity (χ) of the B-complex were calculated using the equations listed in Table 4.
I: Ionization potential = −EHOMO
A: Electron affinity = −ELUMO
ΔΕgap: Energy gap = EHOMO − ELUMO
χ: Absolute electronegativity = (I + A)/2
η: Global hardness = (I − A)/2
σ: Global softness = l/η
μ: Chemical potential = − χ
ω: Electrophilicity = μ2/2η		(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)

3.5. FT-IR and DFT-IR Spectroscopy

The experimental FT-IR and DFT-IR calculations spectra of the [NՈNBF2] complex are illustrated in Figure 7a,b respectively.
In general, several functional groups vibrations that recognized the structure of the desired complex have been recorded. The main functional groups and their exp. and thero. wavenumber values are illustrated as υCOOH (exp. at 3310 cm−1 and DFT at 3770 cm−1), υC-Hph (exp. at 3040 cm−1 and DFT at 3090–3140 cm−1), υC-Halhyl (exp. at 2860–2950 cm−1 and DFT at 3000–3040 cm−1), υC=O (exp. at 1705 cm−1 and DFT at 1800 cm−1), υC=N (exp. at 1550 cm−1 and DFT at 1570 cm−1), υB-N (exp. at1290 cm−1 and DFT at 1355 cm−1), and υB-F (exp. at 1095 cm−1 and DFT at 1220 cm−1). A high degree of compatibility demonstrated by the plotting together of experimental and DFT wavenumbers with 0.972 graphical correlation was recorded as seen in Figure 7c.

3.6. DOS, HOMO→LUMO, e-transfer/TD-SCF/DFT/B3LYP, and Solvents Effect

Figure 8 shows the HOMO and LUMO shapes, energy, and DOS analysis, which were theoretically stimulated in MeOH. The calculations support electron transfer from HOMO→LUMO with ΔEHOMO/LUMO = 2.94 eV (Figure 8a), the ΔE value was also calculated via DOS as another method and found to be 2.95 eV (Figure 8b). Both ΔEHOMO/LUMO and ΔEDOS energy values correspond to an electronic transition in the visible region (≈430 nm). The absorption behavior of the desired B-complex was recorded by UV-visible spectroscopy using an MeOH solvent (Figure 8c). The electron transfers in solution revealed four bands with λmax 255, 308, 363, and 430 nm values, which are assigned to π→π* e-transition localized in the polyheteroaromatic skeleton of the NՈN-ligand. The π−π* transition bands in the complex are in agreement with TD-DFT computations (Figure 8c and Table 5). By applying the TD-DFT at RT and using same solvent, four main bands with λmax 255, 295, 367, and 433 nm values are predicted Figure 8c. The DFT calculations predicted that the lowest energy transition exhibits the highest oscillator strength and corresponds to the electronic transition from HOMO to the LUMO with 433.5 nm, which compares to the experimentally determined absorption at 430 nm. The solvent effect analysis on this absorption band exhibited a blue shift (22 nm) upon increasing the polarity. For a deeper understanding of the electron transfer in the [NՈNBF2] complex, CAM-TD-DFT calculations were carried out using methanol and the same level of calculations as shown in Figure 8c and Table 6. CAM-TD-DFT reflected also four main bands with λmax 225, 254, 325, and 410 nm values; in general, good agreement between the CAM-TD-DFT and TD-DFT was recorded, noting that CAM-TD-DFT showed less wavelength shifts values of their bands and TD-DFT wavelength values are closer to the experimental UV-vis result, as can be seen from Figure 8.
The experimental and TD-DFT solvents’ effect on the electron transition in [NՈNBF2] was evaluated as seen in Figure 9. Due to the poor solubility of the complex, the study was limited to DMSO, CH3CN, CHCl3, and MeOH solvents. Experimentally, no changes on the wavelengths but only a slight change in the intensity of the four packs were detected by changing the solvents, as can be seen in Figure 9. In the TD-DFT, only the two internal peaks have slight changes on the wavelengths and the intensity of the band; the terminal peaks have no effect by changing the solvents, as seen in Figure 9.

4. Conclusions

The [NՈNBF2] difluoride 10-(4-carboxyphenyl)-2,8-diethyl-5,5-difluoro-1,3,7,9-tetra methyl-5H-dipyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinin-4-ium-5-uide B-complex was synthesized in very good yield. The NMR, IR, DFT, and XRD data proved the formation of tetrahedral geometry around the Boron center in the targeted complex. The 1H, 11B, and 19F-NMR successfully supported the symmetrical π-extended phenomena in the BODIPY complex. The XRD/HSA interactions reflected the presence of 2H….O tail-to-tail carboxylic dimer as well as H….F and non-classical H….O H-bonds interactions in the lattice of the B-complex. The DFT/B3LYP/6-311G(d,p) angles and bond distances’ structural parameters were found to be very consistent with XRD parameters. MAC, NPA, GRD, and MEP reflected the presence of both nucleophilic and electrophilic centers in the B-complex. With the help of DOS, HOMO/LUMO, Exp./IR-DFT, and TD-DFT/UV-vis. behaviors of the tetrahedral B-complex were well elucidated.

Author Contributions

Formal analysis, A.A.A. (Abdulrahman A. Alsimaree), N.I.A. and A.A.A. (Abeer A. AlObaid); data curation, O.M.A.; supervision, J.G.K.; validation, M.M.; review and editing, A.Z.; writing I.W. All authors have read and agreed to the published version of the manuscript.

Funding

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The authors extend their appreciation to Paul Gordon Waddell of Newcastle University for his collaboration in the collection of the single crystal X-ray data of the complex.

Conflicts of Interest

The authors declare no conflict of interest.

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Crystals 11 00606 sch001 550
Scheme 1. Synthesis of the [NՈNBF2] complex.
Scheme 1. Synthesis of the [NՈNBF2] complex.
Crystals 11 00606 sch001
Crystals 11 00606 g001 550
Figure 1. (a) Exp. 1H and (b) NMRDB–1H-NMR, (c) 11B-{1H } and (d) GIAO-NMR, (e) 19F-{1H}- and (f) GIAO-NMR in CDCl3.
Figure 1. (a) Exp. 1H and (b) NMRDB–1H-NMR, (c) 11B-{1H } and (d) GIAO-NMR, (e) 19F-{1H}- and (f) GIAO-NMR in CDCl3.
Crystals 11 00606 g001
Crystals 11 00606 g002 550
Figure 2. Tetrahedral of B-complex structures: (a) ORTEP and (b) DFT-optimized.
Figure 2. Tetrahedral of B-complex structures: (a) ORTEP and (b) DFT-optimized.
Crystals 11 00606 g002
Crystals 11 00606 g003 550
Figure 3. (a) Histogram of XRD/DFT bond lengths and its (b) correlation coefficient, (c) Histogram of XRD/DFT angles and its (d) correlation coefficient, (e) Histogram of XRD/DFT dihedral angles and its (f) correlation coefficient.
Figure 3. (a) Histogram of XRD/DFT bond lengths and its (b) correlation coefficient, (c) Histogram of XRD/DFT angles and its (d) correlation coefficient, (e) Histogram of XRD/DFT dihedral angles and its (f) correlation coefficient.
Crystals 11 00606 g003
Crystals 11 00606 g004 550
Figure 4. (a) O-H….O, (b) CMe-H…..F, and (c) CringH….O H-bonds interactions.
Figure 4. (a) O-H….O, (b) CMe-H…..F, and (c) CringH….O H-bonds interactions.
Crystals 11 00606 g004
Crystals 11 00606 g005 550
Figure 5. (a) dnorm HSA map, (b) shape index, and (c) 2D-FP plots.
Figure 5. (a) dnorm HSA map, (b) shape index, and (c) 2D-FP plots.
Crystals 11 00606 g005
Crystals 11 00606 g006 550
Figure 6. (a) MEP at B3LYP/6311G(d,P) level, (b) NPA (---) and MAC (---) charge, and (c) NPA/MAC graphical correlation.
Figure 6. (a) MEP at B3LYP/6311G(d,P) level, (b) NPA (---) and MAC (---) charge, and (c) NPA/MAC graphical correlation.
Crystals 11 00606 g006
Crystals 11 00606 g007 550
Figure 7. (a) Exp. FT-IR, (b) DFT-IR, and (c) Exp./DFT-IR correlation.
Figure 7. (a) Exp. FT-IR, (b) DFT-IR, and (c) Exp./DFT-IR correlation.
Crystals 11 00606 g007
Crystals 11 00606 g008 550
Figure 8. (a) HOMO/LUMO, (b) DOS, and (c) experimental, TD-DFT, and CAM-TD-DFT spectra in MeOH.
Figure 8. (a) HOMO/LUMO, (b) DOS, and (c) experimental, TD-DFT, and CAM-TD-DFT spectra in MeOH.
Crystals 11 00606 g008
Crystals 11 00606 g009 550
Figure 9. Experimental and TD-DFT solvents effect.
Figure 9. Experimental and TD-DFT solvents effect.
Crystals 11 00606 g009
Table
Table 1. [NՈNBF2] crystal refinement data.
Table 1. [NՈNBF2] crystal refinement data.
Empirical Formula C24H27BF2N2O2
Formula weight 424.28
Temperature/K 150.0(2)
Crystal system Triclinic
Space group P-1
a/Å 7.6047(3)
b/Å 7.7074(3)
c/Å 21.7634(10)
α/° 89.751(4)
β/° 84.955(3)
γ/° 83.375(3)
Volume/Å3 1262.16(9)
Z, Z‘ 2, 1
ρcalc g/cm3 1.116
μ/mm−1 0.660
F(000) 448.0
Crystal size/mm3 0.27 × 0.16 × 0.04
Radiation CuKα (λ = 1.54184)
2Θ range for data collection/° 11.558 to 133.652
Index ranges −9 ≤ h ≤ 8, −9 ≤ k ≤ 9, −25 ≤ l ≤ 25
Reflections collected 17660
Independent reflections 4444 [Rint = 0.0465, Rsigma = 0.0367]
Data/restraints/parameters 4444/0/292
Goodness-of-fit on F2 1.025
Final R indexes [I >= 2σ (I)] R1 = 0.0452, wR2 = 0.1163
Final R indexes [all data] R1 = 0.0592, wR2 = 0.1257
Largest diff. peak/hole/e Å−3 0.23/−0.23
Table
Table 2. DFT/XRD bond lengths (Å), angles (o), and dihedral angles (o).
Table 2. DFT/XRD bond lengths (Å), angles (o), and dihedral angles (o).
No.BondXRDDFTNo.BondXRDDFT
1F1B41.397(2)1.401818C5C61.414(3)1.4179
2F2B41.389(2)1.401719C5C151.493(3)1.4927
3O1H10.830(8)0.968120C6C71.387(2)1.3961
4O1C251.264(3)1.355521C6C161.497(3)1.5042
5O2C251.263(2)1.207422C7C101.434(2)1.4341
6N1C31.353(3)1.344123C7C181.496(3)1.5002
7N1C91.399(2)1.396324C8C91.407(2)1.4033
8N1B41.543(3)1.553125C8C101.389(2)1.4033
9N2C51.345(3)1.344226C8C191.493(2)1.4942
10N2C101.400(2)1.396327C12C131.519(4)1.5393
11N2B41.543(3)1.55328C16C171.519(3)1.5393
12C1C21.393(3)1.396229C19C201.385(2)1.3985
13C1C91.419(2)1.434130C19C241.397(2)1.3994
14C1C111.501(3)1.500231C20C211.382(2)1.3904
15C2C31.403(3)1.417932C21C221.395(2)1.3985
16C2C121.505(3)1.504233C22C231.392(3)1.3982
17C3C141.494(3)1.492734C22C251.483(2)1.4877
No.AnglesXRDDFTNo.AnglesXRDDFT
1H1O1C25117(6)106.2628C10C8C19119.0(1)119.27
2C3N1C9108.1(1)108.8929N1C9C1107.9(1)107.55
3C3N1B4126.3(2)125.2930N1C9C8119.6(1)120.13
4C9N1B4125.6(1)125.8231C1C9C8132.5(2)132.32
5C5N2C10108.3(1)108.8932N2C10C7107.5(1)107.55
6C5N2B4126.1(2)125.2933N2C10C8120.1(1)120.13
7C10N2B4125.4(1)125.8234C7C10C8132.4(2)132.32
8C2C1C9106.9(1)106.7335C2C12C13112.5(2)113.71
9C2C1C11124.5(2)124.8636C6C16C17112.2(2)113.7
10C9C1C11128.7(2)128.4137C8C19C20120.7(1)120.37
11C1C2C3107.5(2)107.2638C8C19C24119.6(1)120.42
12C1C2C12127.6(2)127.4839C20C19C24119.6(2)119.21
13C3C2C12124.9(2)125.2540C19C20C21120.5(2)120.55
14N1C3C2109.6(2)109.5741C20C21C22119.9(2)120.01
15N1C3C14122.2(2)121.9242C21C22C23119.9(2)119.61
16C2C3C14128.1(2)128.5143C21C22C25119.9(2)122.33
17N2C5C6109.9(2)109.5744C23C22C25120.2(2)118.06
18N2C5C15122.7(2)121.9245C22C23C24119.8(2)120.21
19C6C5C15127.4(2)128.5146C19C24C23120.2(2)120.41
20C5C6C7107.3(1)107.2647O1C25O2123.3(2)122.26
21C5C6C16125.2(2)125.2548O1C25C22118.1(2)112.86
22C7C6C16127.4(2)127.4849O2C25C22118.6(2)124.88
23C6C7C10107.0(1)106.7350F1B4F2109.5(2)109.76
24C6C7C18124.4(2)124.8651F1B4N1109.4(2)110.01
25C10C7C18128.6(2)128.4152F1B4N2109.5(2)110.19
26C9C8C10121.9(1)121.4853F2B4N1110.6(2)110.19
27C9C8C19119.1(1)119.2554F2B4N2110.6(2)110.02
No.Dihedral anglesXRDDFTNo.Dihedral anglesXRDDFT
1C9N1C3C20.5−0.2232C11C1C2C121.50.98
2C9N1C3C14178.6179.7133C2C1C9N10.40.07
3B4N1C3C2179.1179.8834C2C1C9C8−178−179.78
4B4N1C3C141.8−0.235C11C1C9N1179.4179.99
5C3N1C9C1−0.60.0936C11C1C9C82.10.13
6C3N1C9C8178.1179.9737C1C2C3N1−0.30.26
7B4N1C9C1179.1179.9938C1C2C3C14178.8179.65
8B4N1C9C8−2.3−0.1339C12C2C3N1178179.19
9C3N1B4F165.760.6340C12C2C3C14−3−0.72
10C3N1B4F2−54.9−60.5241C1C2C12C1386.789.5
11C3N1B4N2−175.5−179.8942C3C2C12C13−91.2−89.21
12C9N1B4F1−113.8−119.2643N2C5C6C71.30.22
13C9N1B4F2125.5119.5944N2C5C6C16178.6179.12
14C9N1B4N24.90.2245C15C5C6C7−177−179.69
15C10N2C5C6−1.4−0.1846C5C6C7C18177179.85
16C10N2C5C15177179.7347C16C6C7C10177179.03
17B4N2C5C6174.3179.8148C6C7C10C8−177−179.9
18B4N2C5C15−7.3−0.2749C18C7C10N2−177−179.96
19C5N2C10C710.0850C10C8C9C1177179.8
20C5N2C10C8179.4179.9651C19C8C9N1177179.95
21B4N2C10C7−174.8−179.9252C9C8C10C7−177−179.96
22B4N2C10C83.60.0453C19C8C10N2−177−179.9
23C5N2B4F1−61.9−60.8154C9C8C19C20−177−88.83
24C5N2B4F258.860.3555C10C8C19C2017791.17
25C5N2B4N1179.4179.8256C10C8C19C24−177−88.84
26C10N2B4F1113.1119.1957C8C19C20C21−177−179.97
27C10N2B4F2−126.2−119.6658C8C19C24C23−177−179.93
28C10N2B4N1−5.5−0.1859C20C21C22C25−177−179.94
29C9C1C2C3−0.1−0.260C25C22C23C24−177−179.96
30C9C1C2C12−178.3−179.161C21C22C25O2177179.86
31C11C1C2C3179.8179.8862C23C22C25O1177179.86
Table
Table 3. MAC and NPA charge population.
Table 3. MAC and NPA charge population.
No.AtomMACNPANo.AtomMACNPA
1F−0.29709−0.5358530H0.0913090.18918
2F−0.29348−0.5324831H0.136510.2186
3O−0.26969−0.6235432C−0.18864−0.58366
4H0.2653250.4681633H0.1314350.2136
5O−0.37872−0.6362534H0.0943520.19069
6N−0.43505−0.5622735H0.1331310.22047
7N−0.4279−0.5567136C−0.2127−0.3594
8C−0.105060.0220737H0.1138490.18236
9C−0.19772−0.0998538H0.1161740.18306
10C0.174030.3241439C−0.2293−0.51552
11C0.1765120.3358940H0.0984760.1797
12C−0.19924−0.0979441H0.0997770.17848
13C−0.096590.0301642H0.0977460.17814
14C−0.075290.0344243C−0.16669−0.56563
15C0.2572760.1130844H0.1267680.20287
16C0.2537130.1124245H0.1005120.19281
17C−0.16645−0.5632146H0.1207020.20111
18H0.1271120.2025647C−0.23101−0.00949
19H0.0989940.1918448C−0.03429−0.16719
20H0.1166220.1989249H0.0946390.18222
21C−0.21392−0.3570550C0.009118−0.12842
22H0.114810.1815151H0.0959020.18206
23H0.1141480.1822952C−0.22343−0.14409
24C−0.22818−0.5166353C0.010034−0.10858
25H0.1003670.1792554H0.1067010.19256
26H0.0958440.177455C−0.03609−0.16044
27H0.0974580.1789956H0.0976160.18146
28C−0.19803−0.5838157C0.4007760.79126
29H0.1338920.2160458B0.5029181.19828
Table
Table 4. Calculated GRD quantum parameters.
Table 4. Calculated GRD quantum parameters.
GRDValue
Global total energyET−1415.9090 a.u,
Low unoccupied molecular orbitalLUMO−0.0838 a.u.
High occupied molecular orbitalHOMO−0.1917 a.u.
Energy gapΔEgap0.1080 a.u.
2.941 eV
Electron affinityA2.2803 eV
Ionization potentialI5.2164 eV
Global hardnessƞ2.9361 eV
Global softnessσ0.3406 eV
Chemical potentialμ−3.7484 eV
Absolute electronegativityX3.7484 eV
Electrophilicityω2.3927 eV
Dipole Momentᶙ3.0497 D
Table
Table 5. TD-DFT computations parameters.
Table 5. TD-DFT computations parameters.
No.λmax (nm)Osc. Str. (f)Major Contributions
1433.490.3433HOMO->LUMO (84%)
2389.140.0127H-1->LUMO (34%), HOMO->L+1 (65%)
3367.630.2794H-1->LUMO (56%), HOMO->LUMO (16%), HOMO->L+1 (26%)
4354.340.0495H-2->LUMO (97%)
5308.290.0034HOMO->L+2 (97%)
6296.940.009H-1->L+1 (98%)
7295.840.113H-3->LUMO (88%)
8287.270.0002H-4->LUMO (45%), H-4->L+1 (51%)
9282.250.0012H-2->L+1 (99%)
10277.550.0027H-5->LUMO (97%)
11259.690.0016H-4->LUMO (54%), H-4->L+1 (42%)
12255.000.2109H-6->LUMO (73%), H-3->L+1 (14%)
Table
Table 6. CAM-TD-DFT computations parameters.
Table 6. CAM-TD-DFT computations parameters.
No.λmax (nm)Osc. Str. (f)Major Contributions
1409.59429470.5877HOMO->LUMO (95%)
2326.470.1111H-1->LUMO (93%)
3306.380.0594H-2->LUMO (95%)
4290.050.0263HOMO->L+1 (95%)
5258.940.0032H-6->L+1 (76%), H-6->L+4 (10%)
6254.110.2336H-3->LUMO (93%)
7240.040.0105H-4->LUMO (51%), H-4->L+1 (29%), H-3->L+2 (15%)
8237.180.0224HOMO->L+2 (98%)
9224.290.3417H-5->LUMO (77%), H-3->L+1 (12%)
10221.170.0029H-4->LUMO (39%), H-4->L+1 (28%), H-1->L+1 (23%)
11218.890.0033H-4->L+1 (12%), H-1->L+1 (72%)
12213.610.116H-5->LUMO (13%), H-3->L+1 (64%)
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Alsimaree, A.A.; Alsenani, N.I.; Alatawi, O.M.; AlObaid, A.A.; Knight, J.G.; Messali, M.; Zarrouk, A.; Warad, I. π-Extended Boron Difluoride [NՈNBF2] Complex, Crystal Structure, Liquid NMR, Spectral, XRD/HSA Interactions: A DFT and TD-DFT Study. Crystals 2021, 11, 606. https://doi.org/10.3390/cryst11060606

AMA Style

Alsimaree AA, Alsenani NI, Alatawi OM, AlObaid AA, Knight JG, Messali M, Zarrouk A, Warad I. π-Extended Boron Difluoride [NՈNBF2] Complex, Crystal Structure, Liquid NMR, Spectral, XRD/HSA Interactions: A DFT and TD-DFT Study. Crystals. 2021; 11(6):606. https://doi.org/10.3390/cryst11060606

Chicago/Turabian Style

Alsimaree, Abdulrahman A., Nawaf. I. Alsenani, Omar Mutlaq Alatawi, Abeer A. AlObaid, Julian Gary Knight, Mouslim Messali, Abdelkader Zarrouk, and Ismail Warad. 2021. "π-Extended Boron Difluoride [NՈNBF2] Complex, Crystal Structure, Liquid NMR, Spectral, XRD/HSA Interactions: A DFT and TD-DFT Study" Crystals 11, no. 6: 606. https://doi.org/10.3390/cryst11060606

APA Style

Alsimaree, A. A., Alsenani, N. I., Alatawi, O. M., AlObaid, A. A., Knight, J. G., Messali, M., Zarrouk, A., & Warad, I. (2021). π-Extended Boron Difluoride [NՈNBF2] Complex, Crystal Structure, Liquid NMR, Spectral, XRD/HSA Interactions: A DFT and TD-DFT Study. Crystals, 11(6), 606. https://doi.org/10.3390/cryst11060606

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