Anomalous HalogenâHalogen Interaction Assists Radial

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Anomalous Halogen-Halogen Interaction Assists Radial Chromophoric Assembly M. A. Niyas, Remya Ramakrishnan, Vishnu Vijay, Ebin Sebastian, and Mahesh Hariharan J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b13754 • Publication Date (Web): 11 Feb 2019 Downloaded from http://pubs.acs.org on February 11, 2019

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Journal of the American Chemical Society

Anomalous Halogen-Halogen Interaction Assists Radial Chromophoric Assembly M. A. Niyas‡, Remya Ramakrishnan‡, Vishnu Vijay, Ebin Sebastian and Mahesh Hariharan* School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Vithura, Thiruvananthapuram, Kerala, India 695551 Supporting Information Placeholder ABSTRACT: The design of highly efficient supramolecular architectures that mimic competent natural systems requires a comprehensive knowledge of noncovalent interactions. Halogen bonding is an excellent noncovalent interaction that forms halogen-halogen (X2) as well as trihalogen interacting synthons. Herein, we report the first observation of a symmetric radial assembly of chromophores (R-3c space group) composed of a stable hexabromine interacting synthon (Br6) that further push the limits of our understanding on the nature, role, and potential of noncovalent halogen bonding. Contrary to the destabilization proposed for Type-I X2 interactions, Br6 synthon possessing Type-I X2 interactions exhibit a stabilizing nature owing to the exchange-correlation component. The radial assembly of chromophores is further strengthened by intermolecular throughspace charge transfer interaction. Br6 synthon driven 3-fold symmetric radial assembly render a lattice structure that reminisces the chromophoric arrangement in the light harvesting system 2 of purple bacteria.

Appreciation of intricate arrays of interacting molecules as the driving force for competent natural processes prompted the synthetic design of efficient supramolecular architectures.1 For instance, remarkable 9-fold symmetry exhibited by light harvesting system 2 (LH2) in purple bacteria2 for photosynthesis is an excellent example for the natural design strategy based on noncovalent interactions. Augmented with the 9-fold symmetry, LH2 complexes display ordered hexagonal lattice structure in the native membrane that assists in the higher absorption of photons. Elegant covalent synthetic strategies were utilized to build radial supramolecular scaffolds revealing toroidal delocalization in 6-fold symmetric hexaarylbenzenes.3 Nevertheless, researchers are in the relentless pursuit for noncovalent interaction based cost-effective strategies to construct exquisite supramolecular structures for material applications. Propensity to form interhalogen interactions caused great excitement for noncovalent halogen bonding4 (earlier known as ‘charge-transfer’ bonds5) as a stable, directional interaction. Halogen bonding has been exploited to build splendid supramolecular architectures including anion networks,6 foldamers,7 polymeric assembly,8 cylindrical micellar nanostructures,9 helical assembly,10 anionic honeycomb networks,11 ternary cocrystals12 and supramolecular nanotubes.13 Although rare, pure halogen-halogen interactions (X2) were also used to direct noncentrosymmetric structures,14 build polymeric sheets15 and bending crystals.16 Albeit the classical electrostatic model17 based on amphoteric nature18 and -hole bond19 dominates the explanation for the stability of halogen bonds, the role of hyperconjugation20 and quantum covalency21 has also been recognized as crucial. The role of dispersion and induction forces were also identified to provide large contribution to the stability of halogen

Scheme 1. Schematic representation of different types of dihalogen interactions. (a) Type-I trans dihalogen bonding, (b) Type-I cis dihalogen bonding, (c) Type-II dihalogen bonding, (d) X3 synthon formed by Type-II dihalogen interactions and (e) X6 synthon, where X represents bromine in the present work, formed by Type-I dihalogen interactions. Golden spheres represent halogen atoms. bonds.21a Statistical analyses from Cambridge Structural Database have identified two major types of X2 interactions namely Type-I (trans and cis) and Type-II (Scheme 1).22 Invocation of classical electrostatic potential as the sole stabilizing component attributed Type-I X2 interactions as destabilizing and TypeII X2 interactions as stabilizing directional interactions.23 Recent IUPAC definition of halogen bond24 relies on electrostatic contribution and suggests Type-II X2 as the only true halogen bond.25 Identification of trihalogen interactions (X3 synthon, Scheme 1d)26 added a new dimension to the nature and scope of halogen bonds. Electrostatic model categorized X3 synthon having Type-II geometry as stabilizing Coulombic interaction. In line with our continued efforts in designing crystalline supramolecular scaffolds,27 to our knowledge, we report the first evidence of a stable X6 (Br6) synthon formed by Type-I synergistic interaction, linking six identical bromine atoms, (Scheme 1e) that challenges the most accepted notion of the essential electrostatic nature of halogen bonds. Theoretical evaluations by Cortada et al.28 and Awwadi et al.29 have surmised the minimum energy geometry of Type-I as θ1=θ2=150̊ and the present study provides an experimental realization of Br6 synthon, with the predicted minimum energy geometry, having a component of covalency (exchange-correlation component) in stabilizing the synthon. Stable noncovalent Br6 synthon drives the chromophores to form an elegant radial/starburst assembly in the crystalline state. The radial arrangement is further strengthened by intermolecular charge transfer interactions.

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Imidization of 1,8-dibromonaphthalic anhydride yielded 1,8-dibromonaphthalene(2,6-diisopropylphenyl)imide (NIBr2, Figure 1a).30 Slow evaporation of solvents from 1:3 chloroform:hexane mixture of NIBr2 yielded single crystals with centrosymmetric space group R-3c (Table S1). Molecular structure of NIBr2 in the crystal lattice comprises of a planar naphthalimide moiety with an orthogonal 2,6-diisopropylphenyl group. Single crystal X-ray structure revealed an intermolecular van der Waals31 Br‧‧‧Br (interatomic distance, dBr‧‧‧Br=3.73 Å) interaction in a trigonal assembly of NIBr2 units (Figure 1a). The assembly is further intercalated by three inverted NIBr2 molecules forming a radial arrangement (Figure 1b). Synergistic Br‧‧‧Br interactions between three molecules of NIBr2 concocts a Br6 synthon that exhibits a three-dimensional geometry of triangular prism with square faces (prism with equilateral triangle forming bases and squares forming faces, Figure 1c). Additionally, intermolecular van der Waals C‧ ‧‧O (dC‧‧‧O=3.14 Å) interaction contributes to the three-dimensional packing of crystalline NIBr2. An interesting feature shown by NIBr2 is the existence of higher order trigonal symmetry in its crystal structure while the molecule itself possesses a low symmetry point group (C1). Although similar high-symmetry crystalline architectures were made by the transfer of symmetry from a molecule to the corresponding crystal,32 formation of high-symmetric crystal structures facilitated by noncovalent interactions are rare. The minor role of symmetry and the métier of Br6 synthon in NIBr2 is further pronounced as none of the brominated sister crystals, dibromo acenaphthene (AnBr2,

Figure 2. (a) BCP (green dots), RCP (red dots) and CCP (blue dot) obtained from QTAIM analysis of NIBr2. ESP maps (0.001 isodensity surface) of (b) AnBr2, (c) NIBr2-Pr (d) NIBr and (e) NIBr2. P21/n space group), 4-bromonaphthalene(2,6-diisopropylphenyl)imide (NIBr, P-1 space group) and 1,8-dibromopropylnaphthalimide (NIBr2-Pr, P21 space group) evinced any van der Waals Br‧‧‧Br contacts and/or a high symmetric crystal structure (Figure 1d, e, f).

Figure 1. (a) Trigonal arrangement of NIBr2, (b) radial arrangement of NIBr2, (c) magnified depiction of Br6 synthon. Crystalline packing of (d) AnBr2, (e) NIBr and (f) NIBr2-Pr. CCDC numbers are given in the Supporting Information.

Evidence for noncovalent bond formation in NIBr2 was quantitatively evaluated by Bader’s quantum theory of atoms in molecules (QTAIM) analysis33 (Figure S1). Computed numerical electron density [(r)] and its Laplacian [2(r)] at (3,-1) bond critical point (BCP) suggests the closed shell nature of Br‧‧‧Br, C-H‧‧‧C and C‧‧‧O noncovalent interactions (Table S2). As anticipated, two sets of three bromine atoms at the center of the radial arrangement form a noncovalent equilateral triangular ring that is evident from the (3, +1) ring critical point (RCP). Surprisingly, QTAIM analysis also revealed a (3, +3) cage critical point (CCP) that shows a rare noncovalent cage formed exclusively of bromine atoms (Br6 synthon, Figure 2a). QTAIM analysis establishes the significance of Br‧‧‧Br interaction mediated formation of Br6 cage synthon in contriving the radial arrangement of chromophores (Table S2, Figure S1). Similar RCPs and CCPs were identified in multi halogenated fullerene derivatives.34 Interestingly, QTAIM identified a trihydrogen interaction with an interatomic distance of 2.57 Å. The results from QTAIM is supported by real space noncovalent interaction analysis35 (NCI) where a weak stabilizing interacting region is marked as a green disk in the areas of BCP, RCP and CCP (Figure S2). Low packing efficiency (65.7%) of crystalline NIBr2 is also indicative of the stabilizing and directional nature of Br6 synthon which is in conflict with the argument of close packing as the basis for the occurrence of Type-I X2 interactions.23 Fascinated by the unusual radial arrangement of NIBr2 chromophoric units encompassing Br6 synthon at the center, we


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Journal of the American Chemical Society set out to investigate the nature of Br6 synthon by employing noncovalent interaction energy partitioning through Pendas’ interacting quantum atoms (IQA) approach.36 Although a highly expensive computational technique, IQA provides a reliable atomistic picture of chemical bonding. IQA partitions the total interatomic energy into classical Coulombic component and exchange-correlation component (computational methods, Supporting Information, Table S3). The intermolecular Br‧‧‧Br interaction has a stabilizing total IQA interaction energy (Et) of 4.95 kcal/mol partitioned into a classical Coulombic (Ecl) component of 0.63 kcal/mol and an exchange-correlation (Exc) component of -5.58 kcal/mol. Intramolecular Br‧‧‧Br interaction has a small destabilizing contribution from Ecl (0.50 kcal/mol) and a comparatively large stabilizing component from Exc (17.82 kcal/mol), together contributing to a total interaction energy of -17.32 kcal/mol. The destabilizing Coulombic component is supportive of the traditional wisdom of Type-I halogen-halogen interaction as electrostatically unfavorable. The total interaction energy being stabilizing and the classical Coulombic term exhibiting a destabilizing component points to the significance of covalency caused by the exchange-correlation effect in the noncovalent Br‧‧‧Br interactions. Electrostatic surface potential (ESP) map of NIBr2 was computed and compared with that of AnBr2, NIBr and NIBr2-Pr as controls to uncover the role of electrostatic component in regulating the crystalline packing of NIBr2 (Figure 2). NIBr2 displays an intermediate positive potential at the aromatic core compared to the larger negative potential in that of AnBr2 and higher positive potential in that of NIBr and NIBr2-Pr. Synergetic effect of diisopropylphenyl group and dibromo substituent resulted in the intermediate electrostatic potential at the aromatic core in NIBr2. Electrostatic dipolar interaction37 (Table S4) leads to the antiparallel stacking of chromophores in AnBr2 and NIBr (Figure 1d and e). Electron-rich AnBr2 displays -hole‧‧‧ interactions. Optimal electrostatic potential at the naphthalimide core in NIBr2 thwarts the -hole‧‧‧ (edge to face interaction) and antiparallel stacking thereby favoring the stable Br6 synthon. Albeit the -hole bestowing a destabilizing component (like potential surfaces interacting in Type-I X2), the stabilizing total energy of Br‧‧‧Br interaction shows the inadequacy of classical electrostatics to rationalize the nature of Br‧‧‧Br interactions. The radial assembly in NIBr2 is an exceptional model wherein the competing nature of electrostatics and covalency becomes evident. The UV-Vis absorption spectrum of NIBr2 (Figure 3a) in chloroform displays a →* transition (HOMO-1 → LUMO+1, Figure S3) mostly localized at the naphthalimide core at 300-400 nm. The steady state emission spectrum of NIBr2 in chloroform, excited at 360 nm, exhibits structured emission band with peaks at 394 nm and 413 nm (Fluorescence quantum yield, f= 0.36%). The Kubelka-Munk (K-M) diffuse reflectance spectrum of crystalline NIBr2 displays a broad structured band at 300-400 nm and a distinct weak band centered at 440 nm. The band at 440 nm decreases in intensity upon crushing the crystal suggesting the band originated from intermolecular interactions (Figure S4). The band could be attributed to a weak intermolecular through-space charge transfer (CT) interaction between 2,6diisopropylphenyl and 1,8-dibromonaphthalimide owing to their close proximity in the hexameric unit (Figure 1b). Steady state emission spectrum of crystalline NIBr2, excited at 360 nm, reveals a vibrationally resolved band centered at 370-550 nm (f=0.64%). Emission spectrum with a maximum at 475 nm is obtained on exciting crystalline NIBr2 at the CT band (=440

Figure 3. (a) Absorption and photoluminescence spectra of NIBr2. The inset shows the zoomed in image of phosphorescent bands. (b) fTA spectra of NIBr2. nm) indicating that the CT state contributes to emission of crystalline NIBr2 (Figure S5). The set of weakly intense bands centered at 590 nm and 646 nm in the steady state emission spectrum of crystalline NIBr2 increase in intensity upon recording emission at a time delay of 23 s (lifetime, 590 nm=23 s, Figure S6) and can be ascribed to room temperature phosphorescence (RTP) which is in good agreement with the observed RTP from N-substituted naphthalimides as reported by Zhang and coworkers.38 NIBr2 in ethanol at 77 K exhibits phosphorescence emission which decays with a lifetime of 2.3 ms (Figure S7). Photoexcited state dynamics involved in the population of triplet state was probed using femtosecond (fTA) and nanosecond (nTA) transient absorption measurements. The fTA spectra of NIBr2 in chloroform (Figure 3b) captured the ultrafast intersystem crossing from singlet to triplet state (kisc=7.33 x 1010 s-1) and nTA spectra exhibited spectroscopic signatures of the triplet state39 of the chromophore (t=3.1 s) at 400 nm and 500 nm (see Supporting Information, Figure S8-S9). To conclude, we report the first crystallographic evidence of a stable X6 synthon (Br6) having Type-I dihalogen interaction resulting in a radial arrangement of NIBr2 chromophores in the crystal lattice. The presence of cage critical point in QTAIM complemented by NCI analysis indicate the stabilizing nature of Br6 synthon while IQA revealed exchange-correlation as major contributor towards the stability of Br6 synthon. Our study indicates that Type-I X2 interactions can no longer be ignored as a consequence of close packing. The radial assembly of chromophores is additionally strengthened by an intermolecular charge transfer interaction between the 2,6-diisopropylphenyl moiety and naphthalimide core. Crystalline NIBr2 exhibits RTP with a lifetime of 23 s. As the role of exchange-correlation and hence the covalency has long been overlooked and since the electro-



static model has been demonstrated as insufficient in the present work, the doctrine of classical electrostatics as the exclusive essence of noncovalent halogen-halogen interactions needs to be reassessed.

ASSOCIATED CONTENT

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Supporting Information Supporting Information: Experimental and computational methods, CCDC numbers, tables (Table S1 – S4) and figures (Figure S1 – S9) on QTAIM, NCI, IQA calculations and photophysical measurements (PDF) Crystallographic data for AnBr2, NIBr, NIBr2, NIBr2-Pr (CIF) The Supporting Information is available free of charge on the ACS Publications website.

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AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]

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Author Contributions ‡M. A. Niyas and Remya Ramakrishnan contributed equally.

Notes The authors declare no competing financial interests.

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ACKNOWLEDGMENT M. Hariharan acknowledges Department of Science and Technology (DST), Govt. of India for the support of this work, SR/NM/NS-23/2016(C). We thank Mr. A. P. Andrews for the X‐ ray diffraction analyses, Mr. A. M. Philip for guidance in syntheses and Dr. M. Gudem for guidance in TDDFT calculations. M. A. Niyas and V. Vijay are thankful for DST-INSPIRE Fellowships. R. Ramakrishnan and E. Sebastian acknowledge UGC for financial assistance. Authors thank Prof. A. M. Pendas, University of Oviedo, Spain for fruitful discussions on IQA analysis. Authors thank CSIR-NIIST, Trivandrum, India for phosphorescence measurement facility.

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