Synlett 2019; 30(01): 30-43
DOI: 10.1055/s-0037-1610269
account
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Functional Carbo-benzenes with Functional Properties: The C2 Tether Key

a   CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b   Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
,
Cécile Barthes
a   CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b   Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
,
Arnaud Rives
a   CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b   Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
,
a   CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b   Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
,
a   CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b   Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
› Author Affiliations

The reported results have been obtained with fundings from the following sources: Agence Nationale de la Recherche (ANR-11-BS07-016-01), the Centre National de la Recherche Scientifique (CNRS prematuration program, October 2016-November 2017, PHOTOH2 project), and the Toulouse IDEX program 2015-2017 (CARBO-DEVICE project).
Further Information

Publication History

Received: 11 July 2018

Accepted after revision: 13 August 2018

Publication Date:
12 October 2018 (online)


Abstract

Beyond demonstration of conceptual relevance and synthetic feasibility of aryl/alkyl-substituted representatives, carbo-benzene molecules started to gain prospects of broader impact through the emergence of alkynyl derivatives. This is first illustrated by examples of di- and hexaalkynyl-carbo-benzenes, a carbo-naphthalene, a carbo-biphenyl, and two carbo-terphenyls. A focus is then given to dialkynyl derivatives by reference to the peripherally C2-extruded parents. In the centro­symmetric quadrupolar series, the C2 expansion or ethynylogation effect is more particularly considered for 9H-fluoren-2-yl, tris(O-n-­alkyl)pyrogallyl, indol-3-yl, 4-anilinyl, and tetraphenyl-carbo-phenyl substituents on the following respective properties: two-photon absorption, chemical stability, columnar mesogenicity, on-surface photo­induced charge separation vs single-molecule conductance, and reduction potential. Topical results and prospects of application are discussed on the basis of crystallographic, spectroscopic, and electrochemical analyses vs DFT-calculated nuclear and electronic structures. For the sake of the discussion consistency, complementary experimental and computational results are disclosed in the dianilinyl series. Overall, it is shown that combined advances in strategy, protocols, and substrate scope of acetylenic synthesis remain crucial for the development of yet poorly explored but promising types of molecular materials.

1 Introduction

2 Hexaalkynyl-carbo-benzene

3 ortho-Dialkynyl-carbo-benzene

4 para-Dialkynyl-carbo-benzenes

4.1 Bistrimethylsilylethynyl-carbo-benzene

4.2 Bisfluorenylethynyl-carbo-benzene

4.3 Bistrialkoxyarylethynyl-carbo-benzenes

4.4 Bisindolylethynyl-carbo-benzene

4.5 Bisanilinylethynyl-carbo-benzene

5 Carbo-oligo(phenyleneethynylene)s

6 Conclusions

Supporting Information

 
  • References and Notes


    • For reviews on carbo-mers see:
    • 1a Maraval V, Chauvin R. Chem. Rev. 2006; 106: 5317
    • 1b Cocq K, Lepetit C, Maraval V, Chauvin R. Chem. Soc. Rev. 2015; 44: 6535

    • For the early definition, see:
    • 1c Chauvin R. Tetrahedron Lett. 1995; 36: 397

    • For references invoking the ethynylogation process, see:
    • 1d Hafner K, Neuenschwander M. Angew. Chem., Int. Ed. Engl. 1968; 7: 459
    • 1e Arnold DP, James DA. J. Org. Chem. 1997; 62: 3460
    • 1f Young BS, Herges R, Haley MM. Chem. Commun. 2012; 9441
    • 1g Haley MM, Chase DT, Rose B, Fix AG. US9099660, 2015
    • 1h Listunov D, Saffon-Merceron N, Joly E, Fabing I, Genisson Y, Maraval V, Chauvin R. Tetrahedron 2016; 72: 6697
    • 2a A computational advance in this direction has been undertaken by comparison of ethynylogous OPE[n] and OPP[n], for n = 0–10. For a given π-conjugation extent n C (= 6n + 6 for OPP[n], 8n + 6 for OPE[n]), the HOMO–LUMO gap is found always greater for OPE[(nC–6)/8] than for OPP[(nC–6)/6], becoming greater than 3.2 eV for n C ≥ 54 (corresponding to OPP[8] and OPE[6]). The OPE series is therefore definitely softer than the OPP series vs n C. Calculations for ideal conjugation (under D 2h symmetry constraint) performed at the B3PW91/6-31G(d,p) level with the program Firefly 8.1.1: Granovsky, A. A. Firefly Version 8 http://classic.chem.msu.su/gran/firefly/index.html) which is partially based on the GAMESS (US) source code.
    • 2b Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su S, Windus TL, Dupuis M, Montgomery JA. J. Comput. Chem. 1993; 14: 1347 ; see Supporting Information
    • 3a Kuwatani Y, Watanabe N, Ueda I. Tetrahedron Lett. 1995; 36: 119
    • 3b Suzuki R, Tsukuda H, Watanabe N, Kuwatani Y, Ueda I. Tetrahedron 1998; 54: 2477

      For theoretical studies of carbo-mers, see for example:
    • 4a Godard C, Lepetit C, Chauvin R. Chem. Commun. 2000; 1833
    • 4b Lepetit C, Godard C, Chauvin R. New J. Chem. 2001; 25: 572
    • 4c Ducere J.-M, Lepetit C, Lacroix PG, Heully J.-L, Chauvin R. Chem. Mater. 2002; 14: 3332
    • 4d Lepetit C, Zou C, Chauvin R. J. Org. Chem. 2006; 71: 6317
    • 4e Soncini A, Fowler PW, Lepetit C, Chauvin R. Phys. Chem. Chem. Phys. 2008; 10: 957
    • 4f Chauvin R, Lepetit C, Maraval V, Leroyer L. Pure Appl. Chem. 2010; 82: 769
    • 4g Wodrich MD, Gonthier JF, Steinmann SN, Corminboeuf C. J. Phys. Chem. A 2010; 114: 6705
    • 4h Aspiroz JM, Islas R, Moreno D, Fernández-Herrera MA, Pan S, Chattaraj PK, Martínez-Guajardo G, Ugalde JM, Merino G. J. Org. Chem. 2014; 79: 5463
    • 4i Poidevin C, Malrieu J.-P, Trinquier G, Lepetit C, Allouti F, Alikhani ME, Chauvin R. Chem. Eur. J. 2016; 22: 5295
    • 5a Rives A, Baglai I, Malytskyi V, Maraval V, Saffon-Merceron N, Voitenko Z, Chauvin R. Chem. Commun. 2012; 48: 8763
    • 5b Rives A, Maraval V, Saffon-Merceron N, Chauvin R. Chem. Eur. J. 2012; 18: 14702
    • 5c Rives A, Maraval V, Saffon-Merceron N, Chauvin R. Chem. Eur. J. 2014; 20: 483
    • 6a Barthes C, Rives A, Maraval V, Chelain E, Brigaud T, Chauvin R. Fr.-Ukr. J. Chem. 2015; 3: 60
    • 6b Rives A, Baglai I, Barthes C, Maraval V, Saffon-Merceron N, Saquet A, Voitenko Z, Volovenko Y, Chauvin R. Chem. Sci. 2015; 6: 1139
  • 7 Cocq K, Maraval V, Saffon-Merceron N, Saquet A, Poidevin C, Lepetit C, Chauvin R. Angew. Chem. Int. Ed. 2015; 54: 2703

    • For references on [N]pericyclynes, see:
    • 8a Scott LT, DeCicco GJ, Hyun JL, Reinhardt G. J. Am. Chem. Soc. 1983; 105: 7760
    • 8b Scott LT, DeCicco GJ, Hyun JL, Reinhardt G. J. Am. Chem. Soc. 1985; 107: 6546

    • For references on hexaoxy[6]pericyclynes, see:
    • 8c Maurette L, Tedeschi E, Sermot E, Soleilhavoup M, Hussain F, Donnadieu B, Chauvin R. Tetrahedron 2004; 60: 10077
    • 8d Leroyer L, Zou C, Maraval V, Chauvin R. C. R. Chimie 2009; 12: 412
  • 9 Chauvin R. Tetrahedron Lett. 1995; 36: 401
    • 10a Saccavini C, Sui-Seng C, Maurette L, Lepetit C, Soula S, Zou C, Donnadieu B, Chauvin R. Chem. Eur. J. 2007; 13: 4914
    • 10b Cocq K, Maraval V, Saffon-Merceron N, Chauvin R. Chem. Rec. 2015; 15: 347
    • 11a Cocq K, Saffon-Merceron N, Poater A, Maraval V, Chauvin R. Synlett 2016; 27: 2105
    • 11b Zhu C, Duhayon C, Saquet A, Maraval V, Chauvin R. Can. J. Chem. 2017; 95: 454
    • 11c Zhu C, Rives A, Duhayon C, Maraval V, Chauvin R. J. Org. Chem. 2017; 82: 925
    • 11d Listunov D, Duhayon C, Poater A, Mazères S, Saquet A, Maraval V, Chauvin R. Chem. Eur. J. 2018; 24: 10699
    • 12a Lepetit C, Zou C, Chauvin R. J. Org. Chem. 2006; 71: 6317
    • 12b Zou C, Duhayon C, Maraval V, Chauvin R. Angew. Chem. Int. Ed. 2007; 46: 4337

      For n = 6, see:
    • 13a Diercks D, Armstrong JC, Boese R, Vollhardt KP. C. Angew. Chem., Int. Ed. Engl. 1986; 25: 268
    • 13b Neena TX, Whitesides GM. J. Org. Chem. 1988; 53: 2489
    • 13c Boese R, Green JR, Mittendorf J, Mohler DL, Vollhardt KP. C. Angew. Chem., Int. Ed. Engl. 1992; 31: 1643
    • 13d Haley MM. Pure Appl. Chem. 2008; 80: 519
    • 13e Jia Z, Li Y, Zuao Z, Liu H, Huang C, Li Y. Acc. Chem. Res. 2017; 50: 2470

    • For n = 5, see:
    • 13f Bunz UH. F, Enkelmann V, Rader J. Organometallics 1993; 12: 4745
    • 13g Jux N, Holczer K, Rubin Y. Angew. Chem., Int. Ed. Engl. 1996; 35: 1986
    • 13h Steffen W, Laskoski M, Morton JG. M, Bunz UH. F. J. Organomet. Chem. 2004; 689: 4345

    • For n = 4, see:
    • 13i Bunz UH. F, Enkelmann V. Angew. Chem., Int. Ed. Engl. 1993; 32: 1653
    • 13j Laskoski M, Morton JG. M, Smith MD, Bunz UH. F. J. Organomet. Chem. 2002; 652: 21
    • 13k Esselman BJ, McMahon RJ. J. Phys. Chem. A 2012; 116: 483
    • 13l Thompson SJ, Lee Emmert III F, Slipchenko LV. J. Phys. Chem. A 2012; 116: 3194
    • 13m Burgun A, Gendron F, Schauer PA, Skelton BW, Low PJ, Costuas K, Halet J.-F, Bruce B, Lapinte C. Organometallics 2013; 32: 5015

    • For n = 4 and 8, see:
    • 13n Yavari I, Jabbari A, Samadizadeh M. J. Chem. Res., Synop. 1999; 152

    • For n = 3, see:
    • 13o Domnin IN, Takhistov VV, Ponomarev DA. Eur. Mass Spectrom. 1999; 5: 169
    • 13p Morton MS, Selegue JP. J. Organomet. Chem. 1999; 578: 133
  • 14 Basic calculations of the heterolytic bond dissociation energy ΔE(R), corresponding to the equation (MeC≡C)2RC–OH → (MeC≡C)2RC+ + OH in the gas phase, show that ∆E(MeC≡C) – ΔE(Ph) = +3 kcal/mol: ΔE(MeC≡C) = 0.32935 Ha, ΔE(Ph) = 0.32458 Ha, ΔE(Me) = 0.34930 Ha, ΔE(H) = 0.36285 Ha. Calculations at the B3PW91/6-31G(d,p) level with the program Firefly 8.1.1: see ref. 2a,b.
    • 15a Nicholas KM.  Acc. Chem. Res. 1987; 20: 207
    • 15b McGlinchey MJ, Girard L, Ruffolo R. Coord. Chem. Rev. 1995; 143: 331
    • 15c Melikyan GG, Bright S, Monroe T, Hardcastle KI, Ciurash J. Angew. Chem. Int. Ed. 1998; 37: 161
  • 16 Karadakov PB. Chem. Phys. Lett. 2016; 646: 190
  • 17 Cocq K, Saffon-Merceron N, Coppel Y, Poidevin C, Maraval V, Chauvin R. Angew. Chem. Int. Ed. 2016; 55: 15133
  • 18 Saccavini C, Tedeschi C, Maurette L, Sui-Seng C, Zou C, Soleilhavoup M, Vendier L, Chauvin R. Chem. Eur. J. 2007; 13: 4895
  • 19 For the preparation of dibenzoylacetylene 12, see: Zhang ZZ, Schuster GB. J. Am. Chem. Soc. 1989; 111: 7149
    • 20a Hrobárik P, Hrobáriková V, Semak V, Kasák P, Rakovský E, Polyzos I, Fakis M, Persephonis P. Org. Lett. 2014; 16: 6358
    • 20b Tran C, Berqouch N, Dhimane H, Clermont G, Blanchard-Desce M, Ogden D, Dalko PI. Chem. Eur. J. 2017; 23: 1860
  • 21 Belfield KD, Yao S, Bondar MV. Adv. Polym. Sci. 2008; 213: 97
  • 22 Baglai I, de Anda-Villa M, Barba-Barba RM, Poidevin C, Ramos-Ortíz G, Maraval V, Lepetit C, Saffon-Merceron N, Maldonado J.-L, Chauvin R. Chem. Eur. J. 2015; 21: 14186
  • 23 For a recent review on discotic liquid crystals, see: Wöhrle T, Wurzbach I, Kirres J, Kostidou A, Kapernaum N, Litterscheidt J, Haenle JC, Staffeld P, Baro A, Giesselmann F, Laschat S. Chem. Rev. 2016; 116: 1139
  • 24 Rives, A.; Maraval, V.; Chauvin, R. unpublished results.
  • 25 Zhu C, Wang T.-H, Su C.-J, Lee S.-L, Rives A, Duhayon C, Kauffmann B, Maraval V, Chen C.-h, Hsu H.-F, Chauvin R. Chem. Commun. 2017; 53: 5902
  • 26 Wu J, Warson MD, Zhang L, Wang Z, Müllen K. J. Am. Chem. Soc. 2004; 126: 177
  • 27 Rives A, Baglai I, Malytskyi V, Maraval V, Saffon-Merceron N, Voitenko Z, Chauvin R. Chem. Commun. 2012; 48: 8763
  • 28 Baglai I, Maraval V, Bijani C, Saffon-Merceron N, Voitenko Z, Volovenko YM, Chauvin R. Chem. Commun. 2013; 49: 8374
  • 29 Baglai I, Maraval V, Duhayon C, Chauvin R. Acta Crystallogr., Sect. E: Struct. Rep. Online 2013; 69: o921
    • 30a Bhattacharya A, Vasques T, Ramirez T, Plata RE, Wu J. Tetrahedron Lett. 2006; 47: 5581
    • 30b Nemoto H, Fujita S, Nagai M, Fukumoto K, Kametani T. J. Am. Chem. Soc. 1988; 110: 2931
  • 31 Experimental Procedure and Characterization of 27b First StepBis(benzonitrile)palladium(II)chloride (41.3 mg, 0.107 mmol) and CuI (9.6 mg, 0.074 mmol) were placed into a Schlenk tube under argon and dissolved in 4 mL of dry 1,4-dioxane. The mixture was then treated with tri-tert-butylphosphine (0.22 mL, 1 M solution in toluene, 0.22 mmol) at r.t. After the solution turned black, distilled diisopropylamine (0.65 mL, 4.99 mmol), 4-bromo-N,N-bis(trimethylsilyl)aniline (1.0 mL, 3.54 mmol) and trimethylsilylacetylene (0.65 mL, 4.60 mmol) were added. The resulting mixture was heated at 50 °C for 2 h, and then cooled down to r.t. before addition of EtOAc, filtering through Celite®, and concentration under reduced pressure to afford 29 as a black sticky liquid (1.42 g), which was used without further purification.Second StepA solution of the crude product 29 (1.42 g) in methanol (20 mL) was cooled down to 0 °C, before treatment with K2CO3 (884 mg, 6.40 mmol). The resulting mixture was stirred for 1 h at 0 °C before addition of distilled water (20 mL). Then, the methanol was removed under reduced pressure. The remaining aqueous layer was extracted with Et2O, and the combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure to afford 27b as a spectroscopically pure brown viscous liquid (920 mg, 3.50 mmol, 98% yield over 2 steps). Analytical Data 1H NMR (400 MHz, 298 K, (CD3)2CO): δ = 0.10 (s, 18 H, -Si(CH3)3), 3.7 (s, 1 H, ≡CH) 6.96 (d, 3 J HH = 8.0 Hz, 2 H, o-C6H4–), 7.39 (d, 3 J HH = 8.0 Hz, 2 H, m-C6H4–) ppm. 13C{1H} NMR (100 MHz, 298 K, (CD3)2CO): δ = 1 .31 (–Si(CH3)3), 77.66 (–C≡C–H), 83.37 (–C≡C–H), 117.54 (ipso-C6H4), 130.28 (o-C6H4), 132.77 (m-C6H4), 149.08 (p-C 6H4) ppm.
  • 32 Experimental Preparation and Characterization of 1p First StepA solution of 27b (638 mg, 2 .44 mmol) in dry THF (15 mL) was treated at –78 °C with lithium bis(trimethylsilyl)amide (2.8 mL, 1 M solution in THF, 2.8 mmol). The resulting mixture was stirred for 1 h at –78 °C before dropwise addition of a solution of 16 (706 mg, 1.04 mmol) in dry THF (60 mL) at the same temperature. The resulting mixture was allowed to warm up to r.t. under stirring over 18 h. After treatment with a saturated aqueous solution of NH4Cl and extractions of the aqueous layer with Et2O, the combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure to afford the diol 28b as an orange solid (1.48 g), which was used without further purification.Second StepA solution of the crude 28b (1.48 g) in dry DCM (330 mL) was treated at –78 °C with SnCl2 (2.43 g, 12.8 mmol) and HCl·Et2O (12.4 mL, 2 M solution in Et2O, 24.8 mmol). The resulting mixture was allowed to warm up to –15 °C under stirring over 3.5 h, and then kept for 10 min. at r.t. before addition of NaOH (25 mL, 2 M aqueous solution, 50 mmol). The resulting mixture was stirred at r.t. for 16 h. After treatment with a saturated aqueous solution of Na2CO3 and extractions of the aqueous layer with DCM, the combined organic layers were dried over anhydrous MgSO4 before filtration through Celite® and concentration under reduced pressure. Washings of the crude solid with pentane and Et2O afforded the expected carbo-benzene 1p as a dark violet solid (160 mg, 0.21 mmol, 20% yield over 2 steps).Analytical Data 1H NMR (400 MHz, 298 K, (D8-THF)): δ = 5.38 (br s, 4 H, –NH2), 6.83 (3 J HH = 8.0 Hz, 4 H, m-C6 H 4–NH2), 7.70 (t, 3 J HH = 8.0 Hz, 4 H, p-C6H5), 7,80 (d, 3 J HH = 8.0 Hz, 4 H, o-C6 H 4–NH2), 7.98 (t, 3 J HH = 8.0 Hz, 8 H, m-C6H5), 9.47 (t, 3 J HH = 8.0 Hz, 8 H, o-C6H5) ppm. 13C{1H} NMR (100 MHz, 298 K, (D8-THF)): δ = 87.00–113.90 (–C≡C– and >C≡C≡C≡C<), 115,16 (m-C6H4–NH2), 119,85, 120,81 (>C(C6H4–NH2)– and >C(C6H5)–), 130.00–130.84 (o, m, p-C6H5), 134.85 (o-C6H4–NH2), 140.33, 152.07 (p-C6H4–NH2 and p-C6H5) ppm. MS (MALDI-TOF/DCTB): m/z (%) = 756.2 (100) [M]+.HRMS (MALDI-TOF/DCTB): m/z [M]+ calcd for C58H32N2: 756.2565; found: 756.2602; [M + Na]+ calcd for C58H32N2Na: 779.2463; found: 779.2437. UV-vis (THF): λmax(ε) = 493 nm (131000 L/mol/cm). Voltammetry: reduction: E (V/SCE) = –0.67 (rev), –1.09 (rev), –1.56 (irrev), oxidation: 0.74 (irrev).
    • 33a Li Z, Smeu M, Rives A, Maraval V, Chauvin R, Ratner MA, Borguet E. Nature Commun. 2015; 6: 6321

    • For the STM-break junction method, see:
    • 33b Xu BQ, Tao NJ. Science 2003; 301: 1221
  • 34 Choi SH, Kim BS, Frisbie CD.  Science 2008; 320: 1482
    • 35a Cure J, Kahn M, Cocq K, Casterou G, Chauvin R, Maraval V. FR 1660040, 2016
    • 35b Cure J, Kahn M, Cocq K, Casterou G, Chauvin R, Maraval V, Assi H. PCT/FR 2017/052842, 2017
  • 36 Zhu C, Poater A, Duhayon C, Kauffmann B, Saquet A, Maraval V, Chauvin R. Angew. Chem. Int. Ed. 2018; 57: 5640

    • See for example:
    • 37a Lu Q, Yao C, Wang X, Wang F. J. Phys. Chem. C 2012; 116: 17853
    • 37b Parker CR, Leary E, Frisenda R, Wei Z, Jennum KS, Glibstrup E, Abrahamsen PB, Santella M, Christensen MA, Della Pia EA, Li T, Gonzalez MT, Jiang X, Morsing TJ, Rubio-Bollinger G, Laursen BW, Nørgaard K, van der Zant H, Agrait N, Brønsted NielsenM. J. Am. Chem. Soc. 2014; 136: 16497