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Catalytically Active Coordination Polymer with a Tiny Zn2se2 Ring Bridged by Bis-Selone

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Catalytically Active Coordination Polymer with a Tiny Zn2se2 Ring Bridged by Bis-Selone RSC Advances View Article Online PAPER View Journal | View Issue Catalytically active coordination polymer with a tiny Zn Se ring bridged by bis-selone† Cite this: RSC Adv., 2020, 10, 28950 2 2 Mannarsamy Maruthupandi and Ganesan Prabusankar * Received 23rd May 2020 The unprecedented architecture of a one-dimensional coordination polymer with a tiny Zn2Se2 ring system Accepted 23rd July 2020 incorporated in the hydrogen-bonded array has been prepared, where the di-selone ligand functions as DOI: 10.1039/d0ra04577b a unique neutral bridging ligand. The coordination polymer shows excellent catalytic activity in substituted 8-hydroxy-2-quinolinyl synthesis through Knoevenagel condensation reaction. rsc.li/rsc-advances Later we developed the homoleptic and heteroleptic zinc(II) Introduction III III ¼ selones, [Zn(L )2X2](L 1-methyl 3-naphthyl-methyl imid ¼ IV 0 0 ¼ Imidazoline selones have been considered as a neutral s donor azoline-2-selone), (X Cl or Br), [{Zn(L )4}{X }2](X BF4 or IV IV ¼ ligand that can be an ideal choice to replace the N-heterocyclic ClO4), and [Zn(L )2Br2](L 1-isopropyl 3-methylimidazoline-2- 1–4,5a 5 Creative Commons Attribution-NonCommercial 3.0 Unported Licence. carbene (NHC) type ligands in catalysis. To date, many selone) catalysed thioetheri cation of aryl halides. Recently we V metal complexes bearing imidazole selone ligands have been developed the mesoionic chalcogenone zinc(II) complexes [(L ) V m2 VI ¼ prepared to understand the potential role in catalysis. Since Zn(Cl)2(HOMe)], [(L )Zn(Br)( -Br)]2,[(L )Zn(X)2(HOMe)] (X Cl VII m2 V ¼ imidazole-2-selones can donate up to six electrons with multiple or Br), [(L )Zn(Br)( -Br)]2 and (L 1-(2-mesitylene)-3-methyl-4- coordination modes, various coordination patterns have been phenyltriazolin-5-selone; LVI ¼ 1-(2-mesitylene)-3-methyl-4-phenyl observed.5b,5e Similar such new coordination modes of a multi- triazolin-5-thione; LVII ¼ 1-(benzyl)-2-3(methyl)-4-phenyltriazolin- dentate ligand can bring a new strategy to construct novel 5-selone), for thioetherication reactions.6 These catalysts were coordination polymers. Like NHC, imidazole selone ligated highly active towards the cross-coupling reaction between aryl metal clusters or polynuclear assemblies are rare due to the halides and thiophenols without scrubbing oxygen. However, the This article is licensed under a steric inuence of a N-substituent at imidazole-2-selone.3 Among transition metal derivatives of imidazole-2-selone, the catalytic application of Zn(II)-imidazole selone is lest studied 4–6 Open Access Article. Published on 04 August 2020. Downloaded 9/26/2021 8:59:34 AM. due to the formation of insoluble ill-de ned material. The isolation of structurally characterized coordination polymers of Zn(II)-imidazole selone is the most challenging task.7 In general, the zinc(II) coordination polymers have demon- strated to their potential applications in catalysis, electrochemistry as conducting materials and optoelectronics.8 However, only one structural investigation on bis-azole thione bridged zinc(II) coor- dination polymer has been reported.4–7 The similar class of zinc selones and their catalytic applications are still in the embryonic stage, and their coordination polymers are particularly rare I (Scheme 1). We have reported the rst zinc(II) selone, [{(L )2Zn} I {ClO4}2$2H2O] (L ¼ 3-(2-methoxy-2-oxoethyl)-1-mesityl-imidazo II 2+ 2À II line selone) and [{(L )4Zn} {ClO4}2 ](L ¼ 1-(2,6- diisopropylphenyl)-3-(2-methoxy-2-oxoethyl)-imidazoline selone) mediated Barbier coupling reactions in aqueous alcohol media.4 Department of Chemistry, Indian Institute of Technology Hyderabad, 502 285, India. E-mail: [email protected] † Electronic supplementary information (ESI) available: FT-IR, 1H NMR, and 13C NMR spectra along with solid-state packing and sample under UV-vis light of $ reported molecules. CCDC 2005360 (L H2O) and 2005361 (1). For ESI and Scheme 1 Known zinc(II) imidazoline chalcogenone mediated cata- crystallographic data in CIF or other electronic format see DOI: lytic reactions. 10.1039/d0ra04577b 28950 | RSC Adv.,2020,10,28950–28957 This journal is © The Royal Society of Chemistry 2020 View Article Online Paper RSC Advances application of structurally characterized zinc(II) complexes based disordered (vide infra). The coordination mode of the bis-selenium on bridging azo-selone ligands are scarce. ligand in 1 is quite rare for zinc(II)-selones. The zinc centers and Our interest is in the synthesis of new zinc coordination selenium atoms of the bridging organo selenium ligand are polymers containing bis-selone ligand. To enhance the struc- located in the same plane (F of Zn1–Se1–Zn1#–Se1#]0). That is, tural multifariousness, the incorporation of exible ethyl spacer Zn2Se2 shows a synperiplanar conformation. Two selenium atoms containing bis-selone into the zinc selone structure is highly of the benzimidazole groups from L bridges between zinc(II)center desired. This investigation has been based on the notion that to form a tiny Zn2Se2 ring. Owing to the strained chelation of the modication of the zinc coordination environment may disrupt selone, an extraordinarily small bond angle of 67.42(9) is observed III the overall structure of the zinc coordination polymer, thus at Se1–Zn1–Se1, which is not comparable with [Zn(L )2Br2] IV 5a altering and/or favoring their catalytic activities. Based on this (102.99(5) ) and [Zn(L )2Br2] (105.58(11) ). approach, we reported the largest copper(I) cubanes with pyri- Since the ethyl bridge of benzimidazole-2-selone can rotate, 3 dine bridged bis imidazole-2-selone. This result shows that the L acts as a pliable connector between the zinc centers of Zn2Se2 ligand demonstrates a peculiar ability to formulate the cubanes, rings. Each ligand connects two zinc(II) centers to yield a one- and the results also indicated that the exible alkane spacer dimensional structure with a small ring cavity (about 4.9 A) in plays a signicant role in directing the cluster structures and the ab plane (Fig. 3). Interestingly, the zinc center of 1 features topologies. To further investigate the inuence of the neutral a highly distorted tetrahedral structure with the selenium ligands and alkane spacer on the formation of supramolecular bridging atom in the basal position, and the apical plane architectures, we focus on synthesizing a new bis- positions are occupied by two bromine ligands. The Zn1–Se1 benzimidazole selone ligand, and we report the reaction bond lengths (2.494(4) A) is comparable to the known complex 0 III 5a between ZnBr2 and [(3,3 -ethane)bis(1-isopropyl-benzimidazole- of a similar type, [Zn2(L )2Br4] (2.476(3) A and 2.491(3) A). The 2-selenone)] (L), which give rise to a catalytically active 1D C]Se bond distance in 1 is 1.866(3) A, which is about 0.046 A coordination polymer [(L){ZnBr2}2]a (1). The coordination longer than that of L due to the good s donor property of the ] Creative Commons Attribution-NonCommercial 3.0 Unported Licence. polymer 1 depicts a new architecture generated by an unusual ligand. The Se(1) C(1) bond lengths in 1 considerably elon- Zn2Se2 ring bridged through the bis benzimidazole selone gated compared to the corresponding ligand L. These one- ligand. dimensional coordination polymers interdigitated each other to afford a layered structure through hydrogen bonds between Results and discussion bromine and CH moieties at diselone ligand. 1 shows both intra- and intermolecular Br/H–C hydrogen bonding interac- $ Synthesis and characterization of L H2O and 1 tions. These hydrogen bonding interactions connect the 1D $ The selone ligand L H2O was isolated with excellent yield from coordination polymer to the self-assembled 2D stacking array of the reaction between 1,10-(ethane)bis(3-isopropyl- a layered structure. This article is licensed under a benzimidazolium) bromide salt with selenium powder in the The thermal stability of coordination polymer 1 was inves- presence of K2CO3 (Scheme 2). L$H2O is entirely soluble in tigated using thermogravimetric analysis under a nitrogen À1 MeOH, DCM, CHCl3, and DMSO, while partially soluble in ethyl atmosphere with a heating rate of 10 C min (Fig. 4). The 1D $ Open Access Article. Published on 04 August 2020. Downloaded 9/26/2021 8:59:34 AM. acetate and insoluble in hexane. The FT-IR spectrum of L H2O coordination polymer shows two-step weight loss with very high À exhibits an intense C]Se stretching frequency at 1164 cm 1.In 13C NMR, the carbon attached with selenium (C]Se) appears at $ 165 ppm. The solid-state structure of L H2O was further conrmed by single-crystal X-ray diffraction technique. The crystallographic data are provided in Table 1. The chalcogenone ligands L$H2O crystallized in monoclinic, space group P21/c. The selected bond lengths and bond angles are listed in Fig. 1. The C]Se bond lengths of L$H2O is 1.820(74) A. The observed C]Se bond length is slightly shorter than that of LI (1.835(3) A), II 4 and L (1.834(3) A). The N–C–N bond angle of L$H2O indicates the existence of sp2 hybridization. The new coordination polymer 1 was synthesized with excel- lent yield from the reaction between zinc bromide, and L$H2O. 1 is partially soluble in MeOH, EtOH, and DMSO. The formation of 1 was conrmed by FT-IR, NMR (1Hand13C), UV-visible, and TGA techniques. 1 crystallized in the monoclinic space group, I2/a. The crystallographic data for 1 are listed in Table 1. The selected bond lengths and bond angles are assembled in Fig. 2. The solid- state structure of 1 reveals a novel 1D coordination polymer based on the assembling of the Zn2Se2 ring.
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