Molecular Recognition by Chalcogen Bond: Selective Chargetransfer Crystal Formation of Dimethylnaphthalene with Selenadiazolotetracyanonaphthoquinodimethane Yusuke Ishigaki, Kota Asai, Henri-Pierre Jacquot de Rouville, Takuya Shimajiri, Valérie Heitz, Hiroshi Fujii-Shinomiya, Takanori Suzuki To cite this version: Yusuke Ishigaki, Kota Asai, Henri-Pierre Jacquot de Rouville, Takuya Shimajiri, Valérie Heitz, et al.. Molecular Recognition by Chalcogen Bond: Selective Chargetransfer Crystal Formation of Dimethyl- naphthalene with Selenadiazolotetracyanonaphthoquinodimethane. European Journal of Organic Chemistry, Wiley-VCH Verlag, In press, 10.1002/ejoc.202001554. hal-03114533 HAL Id: hal-03114533 https://hal.archives-ouvertes.fr/hal-03114533 Submitted on 19 Jan 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Molecular Recognition by Chalcogen Bond: Selective Charge- transfer Crystal Formation of Dimethylnaphthalene with Selenadiazolotetracyanonaphthoquinodimethane Yusuke Ishigaki,[a] Kota Asai,[a] Henri-Pierre Jacquot de Rouville,[b] Takuya Shimajiri,[a] Valérie Heitz,[b] Hiroshi Fujii-Shinomiya,[c,d] and Takanori Suzuki*[a] In memory of François Diederich and Tsutomu Miyashi Abstract: The title nonplanar electron acceptor (1) fused with a selenadiazole ring selectively forms a crystalline charge-transfer complex (CT crystal) with 2,6-dimethylnaphthalene (2,6-DMN). On the other hand, the sulfur analogue (2) has less recognition ability and forms CT crystals with both 2,6- and 2,7-DMN. X-ray analyses of 1, 2, and their CT crystals revealed that the Se ●●● N chalcogen bond (ChB) in 1 is strong enough to determine the crystal packing with the formation of a cavity suitable for 2,6-DMN. On the contrary, ChB through S ●●● N contact in 2 competes with other weak interactions such as a C-H ●●● N hydrogen bond. The stronger ChB involving Se is the key for 1 to separate 2,6-DMN (>97 wt%) from a complex isomer mixture containing ca. 10 wt% each of 2,6- and 2,7-DMN by a simple, efficient and straightforward mixing- filtration-heating process. n(D)→*(E-R) electron donation. Interestingly, E atoms can present two -holes, thus allowing the interaction of two donor Introduction atoms simultaneously. The stability of the ChB is influenced by the nature of the E atom (Te > Se > S >> O), the nature of the Directional short contacts are of primary importance in stabilizing electron-deficient R-group, the R-E ●●● D angle (close to linear) supramolecular systems. Indeed, hydrogen bonds are the most and the Lewis basicity of D.[6] A better understanding of these prevalent stabilizing interaction in biological architectures due to factors has led to application of the ChB in several fields of their directionality and relative strength in comparison to other chemistry, such as supramolecular chemistry[7] and catalysis.[8] weak interactions. However, protein structures can also be Even if the ChB is usually characterized by looking at the sum of stabilized by directional short contacts between a divalent sulfur the van der Waals (vdW) radii in the solid state, this highly [1] and an oxygen atom. More generally, these short contacts directional interaction has scarcely been used in crystal have been conceptualized as the interaction between an engineering of organic compounds.[9] electrophilic chalcogen atom (E) and electron donor atoms (D) acting as a Lewis base.[2] This stabilizing interaction (R-E ●●● D, Crystal engineering takes advantage of intermolecular where R is an electron-withdrawing group) was reported in the interactions in the context of crystal packing to rationalize the solid state in the late 1960's[3] but has gained a renewed interest design of new solids with desired physical and chemical [10] over the last decade. Nowadays, it is referred to as the properties. The crystal is described as the predictable chalcogen bond (ChB).[4] The directionality of the ChB was assembly of molecules into networks of desired geometries, i.e., explained by the existence of at least one -hole on the E atom, a supermolecule.[11] Consequently, the molecular arrangement which defines a positive electrostatic potential region in the in the crystal relies on the nature of the interacting functional direction opposite of the R-E bond.[5] Thus, the E atom acts as a groups, also called supramolecular synthons, between Lewis acid that can be bound by a Lewis base through molecules in the crystal. These supramolecular synthons allow a retrosynthetic approach by the straightforward determination of node connectivity in the crystals. Two major features of [a] Dr. Y. Ishigaki, K. Asai, T. Shimajiri, Prof. Dr. T. Suzuki, supramolecular synthons can be identified: i) their chemical Department of Chemistry, Faculty of Science nature and ii) their relative geometry. Therefore, the use of ChB Hokkaido University, Sapporo 060-0810 (Japan) synthons in crystal engineering is promising due to their high E-mail: [email protected] directionality. The [E ●●● NC] motif is a supramolecular synthon [b] Dr. H.- P. Jacquot de Rouville, Prof. Dr. V. Heitz, [12] Institut de Chimie de Strasbourg, CNRS UMR 7177, Université de of choice since it is chemically robust. We previously used Strasbourg, 4, rue Blaise Pascal, 67000 Strasbourg (France) this supramolecular synthon in tetracyanoquinodimethane [c] Dr. H. Fujii-Shinomiya, Department of Chemistry, Faculty of Science (TCNQ)-type compounds fused with 1,2,5-chalcogenadiazole(s) Tohoku University, Sendai 980-8578 (Japan) (3 – 8, Formula).[13] Interestingly, the linearly-extended [d] On leave from Mitsubishi Oil Company, Co. Ltd. Supporting information for this article is available on the WWW at molecular networks formed by bis(thiadiazolo)-TCNQ (8) in the http://dx.doi.org/10.1002/**** solid state created two-dimensional cavities[14] allowing the separation of (pseudo)centrosymmetric p-disubstituted benzenes from their isomer mixtures by a simple mixing- filtration-heating process (Scheme 1). This report describes the preparation of two new tetracyanonaphthoquinodimethane (TCNNQ) derivatives fused with a chalcogenadiazole ring (1 and 2) and their redox properties.[15] In addition, the selective formation of CT crystals between 1 and 2,6-dimethylnaphthalene (2,6-DMN) towards its 2,7-isomer is demonstrated. Finally, this selective CT crystal formation was used to separate 2,6-DMN from a complex isomer mixture in catalytic reforming petroleum oil. Results and Discussion Molecular design In both derivatives 1 and 2, C≡N ●●● E-N short-contacts were Scheme 1. Simple mixing-fltration-heating process for separation envisioned to drive molecular packing based on favorable of a certain isomer from the mixture as exemplified by separation of geometric and electronic parameters. Indeed, the organization p-disubstituted benzenes from the corresponding isomer mixtures of these supramolecular synthons in the node structure are by electron acceptor 8. expected to lead to decreased steric hindrance in the solid state compared to the well-known chalcogenadiazole square-dimer motif[16] (Scheme 2a,b). In addition, resonance structures reveal an enhanced electron-deficient character of the E atom and an increased electron-donating character of the N atom of the cyano groups in these compounds, which stabilizes the overall assembly (Scheme 2c). Furthermore, both derivatives 1 and 2 have a curved -system and were designed to create three-dimensional cavities in the solid state. These cavities are expected to form CT crystals selectively with fused aromatics such as functionalized naphthalene compounds. Preparation and redox properties of 1 and 2 From the corresponding naphthoquinone derivatives[17] fused with a chalcogenadiazole ring (9 and 10, Formula), yellow crystals of 1 and 2 were obtained upon condensation reactions [18] with malononitrile in the presence of TiCl4 in respective yields of 74% and 89 %. According to DFT calculations for 1 and 2 [M06-2X/6-31G(d,p)], contribution of the polarization form (Scheme 2c) is indicated as shown by the electrostatic potentials (Scheme 2d, Figure S1). Thus, more negative Vs,min (–30.4 and –30.1 kcal mol–1, respectively) is predicted for cyano N atom in 1 and 2 than in TCNNQ (–27.5 kcal mol–1) without a fused heterocycle. Furthermore, the more positive Vs,max values on –1 the chalcogen atoms in 1 and 2 (35.0 and 28.7 kcal mol , respectively) are calculated than in the case of the parent Scheme 2. (a) Connection of two chalcogenadiazolo-TCNQ selenadiazole (19.3 kcal mol–1) and thiadiazole (13.6 kcal mol–1), molecules by ChB through C≡N ●●● E-N contacts. (b) Connection respectively. From the more positive Vs, , stronger ChB is max of two chalcogenadiazoles by ChB through 2N-2E square-dimer- expected in 1 than in 2, which is consistent with previous reports type contacts. (c) Polarization of cyanovinylchalcogenadiazole comparing the ChB in selenadiazole and thiadiazole substructure. (d) Electrostatic potentials in 1 and 2 calculated by [16a] derivatives. DFT method [M06-2X/6-31G(d,p)] (isoval = 0.0004). According to voltammetric analyses in CH3CN (Figure S2), these polycrystalline solid of 2,7-DMN. Thus, thiadiazolo-TCNNQ 2 compounds undergo reversible two-stage one-electron reduction was proven to form CT crystals with both 2,6-and 2,7-DMNs. to give the corresponding dianions. The more negative potentials for 1 (E1 –0.35 V, E2 –0.46 V vs SCE in CH3CN) than To confirm that 1 and 2 show different complexation behavior for 2 (–0.22, –0.41 V) indicates that 1 is a slightly weaker during crystallization but not in solution, the association [19] electron acceptor with a higher LUMO.