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Tetra- and Octapyrroles Synthesized from Confusion and Fusion Approaches

DOI: 10.1021/acs.orglett.6b02495

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Citation for published version (APA): Kong, J., Zhang, Q., Savage, M., Li, M., Li, X., Yang, S., Liang, X., Zhu, W., Ågren, H., & Xie, Y. (2016). Tetra- and Octapyrroles Synthesized from Confusion and Fusion Approaches. Organic Letters, 18. https://doi.org/10.1021/acs.orglett.6b02495 Published in: Organic Letters

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Tetra - and Octapyrroles Synthesized from Confusion and Fusion Approaches

Journal: Organic Letters

Manuscript ID ol-2016-02495b.R1

Manuscript Type: Communication

Date Submitted by the Author: 15-Sep-2016

Complete List of Authors: Kong, Jiahui; East China University of Science and Technology, School of Chemistry and Molecular Engineering zhang, qiong; ShanghaiTech University, School of Physical Science and Technology Savage, Mathew; University of Manchester, Li, Minzhi; School of Chemistry and Chemcal Engineering, Li, Xin; East China University of Science & Technology Yang, Sihai; University of Manchester, School of Chemistry Liang, Xu; Jiangsu University, School of Chemistry and Chemical Engineering Ågren, Hans; Royal Institute of Technology, Laboratory of Theoretical Chemistry Zhu, Weihua; University of Houston, Department of Chemistry; Jiangsu University, School of Chemistry and Chemical Engineering Xie, Yongshu; East China University of Science and Technology, School of Chemistry

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1 2 3 4 Tetra- and Octapyrroles 5 6 Synthesized from Confusion and 7 8 Fusion Approaches 9 10 Jiahui Kong, † Qiong Zhang, ‡ Mathew Savage, ξ Minzhi Li,§ Xin Li, ς Sihai 11 ξ § § ς ,† 12 Yang , Xu Liang, Weihua Zhu, Hans Ågren, and Yongshu Xie* 13 † 14 Key Laboratory for Advanced Materials and Institute of Fine Chemicals, 15 School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China 16 ‡ 17 School of Physical Science and Technology, ShanghaiTech University, Shanghai 200031, China 18 ξ 19 School of Chemistry, University of Manchester, Manchester, m13 9pl, UK § 20 School of Chemistry & Chemical Engineering, Jiangsu University, Zhenjiang 21 212013, China ς 22 Department of Theoretical Chemistry and Biology, School of Biotechnology, 23 KTH Royal Institute of Technology, Stockholm, Se-10691, Sweden 24 [email protected] 25 26 Received Date (will be automatically inserted after manuscript is accepted) 27 28 29 30 ABSTRACT 31 32 33 34 35 36

37 38 By oxidation of an alternately N-confused bilane in CH 2Cl 2, a C-N fused tetrapyrrin (1) was synthesized, which bears a 5.5.5-tricyclic ring generated from intramolecular C-N linkage. When CH CN was used as the reaction medium, a 39 3 multiply C-N fused octapyrrolic dimer (2) was also obtained, which contained two 5.5.5.7.5-pentacyclic moieties and a 40 bipyrrole unit generated from intramolecular C-N linkage and intermolecular C-C linkage, respectively. 1 could 41 coordinate with Ni(acac) 2 to afford a mixed-ligand complex (Ni-1-acac). 42 43 44 45 As a class of promising intermediates in synthetic with one of the terminal α positions blocked with an acyl 46 chemistry,1 and coordinating ligands for substituent (Scheme.1).7 To further enrich the structural 47 constructing supramolecular assemblies 2 and sensing diversity, N-confused units, i.e., α,β’-linked 48 various ions,3 linear oligopyrroles with pyrrole units , may be employed. 8 Thus, a number of bilane 49 interconnected at the α positions have attracted extensive isomers have been reported (Scheme 1, a-e).9-10 Owing to 50 attentions in recent years.4 Tetrapyrrolic bilanes are the higher reactivity of N-confused pyrrole units, 51 unique members of linear oligopyrroles, because they oxidation of these confused bilanes gives rise to a 52 contain the same numbers of pyrrolic units as , diversity of porphyrin analogues. For example, the singly 53 and they have been used for the syntheses of porphyrins N-confused bilanes a and b could be oxidized to afford 54 and their analogues, such as , through confused isomers.9 If two confused pyrrole units 55 acid-catalyzed condensation or oxidative cyclization.5,6 In are introduced, three doubly N-confused bilanes 56 these cases, terminal pyrrole units are interconnected at (Scheme.1, c-e) may be developed. The doubly terminal 57 the free α positions. Supplementary to the macrocyclic confused bilane c and the doubly adjacent confused bilane 58 compounds, we have reported an example of synthesizing d could be oxidatively cyclized to afford corrorin and 59 a linear octapyrrole by oxidative dimerization of a bilane C-fused norrole, respectively. 8d ,10 60 ACS Paragon Plus Environment Submitted to Organic Letters Page 2 of 4

fields. The characters observed for 1 in the NMR and 1 Scheme 1 . Examples of bilanes, confused bilanes and the HRMS were consistent with the intramolecular C-N fused 2 structure (vide infra ), generated from intramolecular corresponding oxidation products (Ar=C 6F5). 3 Ar Ar Ar O oxidative coupling between the NH and α CH moieties. It 4 Ar N Ar N Ar is noteworthy that 1 still contains free α positions. NH HN H H NH HN N 5 Ar Ar Ar Ar N N Especially, the confused pyrrole ring still contains two NH HN N 6 NH HN H H α O N Ar N free positions, which may undergo further fusion or 7 Ar Ar Ar O Ar expansion reactions. Thus, we attempted the further 8 terminally bilane blocked bilane octapyrrole oxidation of 1 with various oxidants. Unfortunately, only 9 Ar Ar Ar Ar H some unidentified decomposed compounds were detected N 10 NH from the reactions. NH HN NH NH HN NH 11 Ar Ar Ar Ar Ar Ar Ar Ar 12 NH NH HN NH N N N N 13 H H H H a b c d Scheme 2. Syntheses of 1 and 2 by oxidation of bilane e with 14 Ar Ar Ar Ar H DDQ in CH Cl and CH CN, respectively, and coordination of 1 15 N 2 2 3 N HN NH NH N HN NH with Ni(II). 16 Ar Ar Ar Ar Ar Ar Ar NH Ar N HN N 17 N N NH HN 18 H 19 corrole isomers corrorin C-fused norrole 20 Ar Ar Ar Ar 21 N HN Ar H N 22 HN N N N Ar Ar N Ar N N Ar N 23 NH NH H Ar N Ar 24 N NH Ar H e 25 1 2 26 27 28 In spite of the excellent examples of porphyrin analogues 29 obtained from the singly and doubly confused bilanes, the 30 oxidation of the alternately N-confused bilane (e) remains 31 unexplored. 11 In this work, simply by oxidizing e, a C-N 32 fused tetrapyrrin (1) and a multiply C-N fused 33 octapyrrolic dimer (2) were obtained, and both an 34 intramolecular C-N linkage and intermolecular C-C 35 linkages were observed. Surprisingly, no porphyrin 36 analogue was obtained at all. To check the possibility of 37 metal coordination, a Ni(II) complex of 1 was also Considering that 1 is already fully conjugated and the 38 synthesized. Despite the abundant examples of reactivity may have been decreased, we returned to check 39 intramolecular ring fusion in porphyrin analogues,12 the oxidation conditions for the precursor e. Interestingly, 40 ring-fused linear oligopyrroles are still quite rare. This when e was oxidized with 3.0 equiv DDQ in CH 3CN 41 work demonstrates the possibility of combined confusion (Scheme 2, Route B), 2 was generated in addition to 1. 42 and fusion approaches for synthesizing novel linear Although 2 was not fully conjugated ( vide infra ), the 43 oligopyrroles applicable in coordination chemistry and further oxidation of 2 with DDQ only afforded some 44 synthetic porphyrinoid chemistry. decomposed compounds. Whereas, 2 was not observed 45 The reaction details are outlined in Scheme 2. Bilane when the reaction was performed in CH 2Cl 2, toluene or + 46 e was first oxidized with 3.0 equiv 2,3-dichloro- THF. The HRMS (2+Na ) of compound 2 (Figure S6) 47 5,6-dicyano-1,4-benzo-quinone (DDQ) in CH 2Cl 2 (Route shows a molecular peak at m/z of 1611.1068, roughly 48 A), affording 1 in a 45% yield. When FeCl 3 or MnO 2 was double of that for e, implying that 2 might be a dimerized 1 49 used as the oxidant, no identifiable compound could be form of e. The H NMR spectrum of 2 (Figure S3) 50 obtained. exhibits a symmetrical structure, bearing only two NH 51 Compound 1 was characterized using NMR protons at 8.27 ppm, consistent with the presence of 52 spectroscopy and HRMS (Figures S1, S4). The parent ion multiple fused rings generated by forming interpyrrolic 53 of 1 was observed at m/z of 797.0822, which was C-N bonds. 54 identical with that calculated from the corrole-like To further elucidate the chemical structures of 1 and 2, 1 13 55 framework. However, the H NMR spectrum of 1 in we successfully obtained their single crystals. X-ray 56 CDCl 3 at 298K revealed nine pyrrolic CH signals in the crystallographic analysis reveals that 1 contains a linear 57 range of 6.0–7.3 ppm and two NH signals at 8.46 and fully conjugated tetrapyrrolic framework (Figure 1a). The α 58 10.60 ppm, totally different from those observed for -carbon of the middle confused pyrrole ring B and the 59 aromatic corrole-like macrocycles which exhibit inner atom of adjacent regular pyrrole ring C are 60 NH signals at higher fields and peripheral CH at lower oxidatively linked through a C-N bond, affording a ACS Paragon Plus Environment Page 3 of 4 Submitted to Organic Letters

5.5.5-tricyclic fused ring, which is nearly coplanar with Considering that compound 1 contains a dipyrrin unit 1 the terminal pyrrole ring A, and the terminally confused composed of pyrroles A and B, it may be employed as a 2 pyrrole D is titled from this plane with a dihedral angle of bidentate ligand to coordinate with metal ions. Consistent 3 36.4°, probably because of the steric hindrance associated with this expectation, when 1 was treated with 4 with the β hydrogen atoms from these two pyrroles. Ni(acac) 2·2H 2O for 10 hours in CH 3CN at reflux, the 5 Within the molecule, N2 is hydrogen bonded to H1 with color of the solution gradually changed from light brown 6 N2…N1 distance of 2.770(7) Å. The molecular structure to dark brown. Thus, a mixed-ligand nickel complex 7 of compound 2 was also unambiguously elucidated by Ni-1-acac was obtained in a 88% yield (Scheme 2). In the 8 X-ray crystallographic analysis (Figure 1b). As expected, 1 H NMR spectrum of Ni-1-acac , the NH peak observed 9 2 has an octapyrrolic structure, generated by linking two for 1 at 10.60 ppm has disappeared (Figure S2), indicative 10 tetrapyrrolic units of e at the α positions of the terminally of the coordination of the dipyrrin moiety. The signals at 11 confused pyrroles. Within each tetrapyrrolic unit, the two 5.32 and 1.77 ppm could be assigned to the coordinated 12 central pyrroles and the terminally confused pyrrole are acetylacetonate ligand. Consistently, the crystal structure 13 fully conjugated and fused by forming two interpyrrolic of Ni-1-acac (Figure 1c) reveals that the Ni(II) atom is 14 C-N bonds. Thus, fusion of pyrroles B, C and D affords a coordinated with two N atoms from 1 and two O atoms 15 nearly planar 5.5.5.7.5-pentacyclic moiety. It is from acac, thus affording a square planar coordination 16 noteworthy that the two terminal regular pyrrole rings in environment, with Ni-N and Ni-O distances of 1.869, 17 2 are linked with the pentacyclic moieties through sp 3 1.929, 1.866, and 1.834 Å, respectively. 18 meso -carbon atoms, which can be clearly evidenced by 19 the bond distances and angles around C5, lying within the 20 ranges of 1.489-1.529 Å and 109.9-112.6°, respectively. 21 As a result, pyrrole A is tilted from the pentacyclic 22 moiety with a large dihedral angle of 55.4°, which also 23 indicates that these two moieties are not fully conjugated. 24 25 26 27 28 29 30 31 32 Figure 2. UV-vis-NIR spectra of 1, 2, and Ni-1-acac in CH 2Cl 2. The inset shows the phtographs of these compounds in CH 2Cl 2. 33 34 35 36 The absorption spectra of 1, Ni-1-acac and 2 are 37 shown in Figure 2. Compound 1 exhibits a strong absorption at 452 nm and a weak peak at 653 nm, 38 assignable to HOMO –› LUMO+1 and HOMO –› LUMO, 39 respectively (Table S3). Ni-1-acac shows split peaks at 40 446 and 553 nm, consistent with HOMO –› LUMO+1 41 and HOMO-1 –› LUMO, respectively. In addition, 42 shoulder peaks appear at 632 and 682 nm. In contrast to 43 the singly fused tetrapyrrin 1, the absorption of the more 44 conjugated dimer 2 is obviously red-shifted, exhibiting a 45 relatively strong and broad peak at 719 nm corresponding 46 to HOMO –› LUMO, which may be related to its larger 47 π-conjugation structure as well as the multiply fused 48 structure. Moreover, the absorption spectra measurements 49 Figure 1. Complementary views of the crystal structures of revealed that all the compounds are quite stable under 50 compounds 1 (a), 2 (b) and Ni-1-acac (c). C 6F5 groups and the 2 diverse conditions expect that Ni-1-acac was 51 hydrogens attached to sp carbons are omitted for clarity. demetallated upon adding TFA (Figures S10-S18).

52 In order to investigate the redox behavior of 53 compounds 1, 2 and Ni-1-acac , the electrochemical 54 The formation of 2 may be attributed to the effect of properties were analyzed with cyclic voltammetry in 55 the more polar solvent, which favors the proton-transfer 14 CH 2Cl 2 containing 0.1 M tetra-n-butylammonium 56 related oxidation reactions. The successful synthesis of perchlorate (TBAP). Compound 1 displays one reduction 57 compounds 1 and 2 indicates that novel linear and two oxidation processes (Figure S8). Similar behavior 58 oligopyrroles may be developed by combining the was observed for compounds 2 and Ni-1-acac . The 59 confusion and oxidative fusion and coupling approaches. electrochemically obtained HOMO-LUMO gaps were 60 ACS Paragon Plus Environment Submitted to Organic Letters Page 4 of 4

found to be 1.88, 1.41 and 2.23 eV for 1, 2 and Ni-1-acac , Supporting Information Available: Complete 1 respectively, under the given experimental conditions. experimental details; crystallographic details (CIF) for 1, 2 To gain further insight into the distribution of the Ni-1-acac and 2; spectroscopic and analytical data, details 3 energy levels, density functional theory (DFT) on DFT calculations. This material is available free of 4 calculations were carried out using the Gaussian 09 charge via the Internet at http://pubs.acs.org. 5 program package. 15 The optimized structures were 6 obtained and the HOMO−LUMO gaps of 1, 2 and 7 Ni-1-acac were calculated to be 2.23, 1.56, and 2.24 eV, 8 respectively (Tables S1. S2). Relative to compound 1, the The authors declare no competing financial interest. 9 octapyrrolic 2 has a larger π-conjugation framework,

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C , 57 Special Appointment (Eastern Scholar, GZ2016006) at 2013 , 1, 7866 (b) McRae, R.P.; Schenter, G.K.; Garrett, B.C.; Svetlicic, Shanghai Institutions of Higher Learning, and the Z.; Truhlar, D.G. J. Chem. Phys , 2001 , 115 , 8460 58 (15) All the calculations were achieved with Gaussian09 program 59 Fundamental Research Funds for the Central Universities (WK1616004). package. See Supporting Information for more details. 60 ACS Paragon Plus Environment