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Solid state photodimerization in an organic salt of 1,2-bis(4-pyridyl)ethylene and trifluoromethane sulphonic acid via pedal-like motion

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Abstract

A novel organic salt, [bpeH].TFMS (1), of trans-1,2-bis(4-pyridyl)ethylene (bpe) was synthesized using trifluoromethane sulphonic acid (\(\hbox {CF}_{3}\hbox {SO}_{3}\hbox {H}\), TFMS) by self-assembly and its crystal structure was determined by X-ray crystallography. Compound 1 forms hydrogen-bonded assembly of [bpeH]\(^{+}\) cations and \(\hbox {CF}_{3}\hbox {SO}_{3}^{-}\) anions which are held together by N–H\({\cdots }\)N, C–H\({\cdots }\)O and C–H\({\cdots }\)F hydrogen-bonding interactions. An attempt has been made to orient the olefinic C=C bonds of bpe in the organic salt via weak hydrogen-bonding interaction for photodimerization reaction in the solid state. The \([\hbox {bpeH}]^{+}\) cations are in parallel orientation in the infinite one dimensional (1D) chain through N–H\({\cdots }\)N hydrogen bonding. The olefinic C=C bonds of bpe are aligned in criss-cross orientation with a center-to-center distance of 4.97 Å. Even though the distance and the orientation of olefinic C=C bonds do not conform with the Schmidt topochemical criteria, compound 1 undergoes photodimerization reaction in solid state to produce stereo-specific rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) (2) in 100% yield. The photoreactivity is expected to take place through cooperative movement of 1D chains and pedal-like motion of the pyridyl rings over the double bonds. The photodimerized product 2 undergoes acid-catalyzed isomerization to produce other cyclobutane isomers such as rcct-tpcb and rtct-tpcb. This strategy for synthesizing organic salts is a facile step for the synthesis of cyclobutane derivatives.

Graphical Abstract

SYNOPSIS A novel organic salt of trans-1,2-bis(4-pyridyl)ethylene and trifluoromethane sulphonic acid was characerized by X-ray crystallography. The salt shows unusual photoreactivity via pedal-like motion of C=C double bonds which change from criss-cross to parallel orientation. The photodimerized product undergoes acid-catalyzed isomerization in solution and produces all the isomers of tetrakis(4-pyridyl)cyclobutane.

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References

  1. (a) Ramamurthy V and Venkatesan K 1987 Photochemical reactions of organic crystals Chem. Rev. 87 433; (b) MacGillivray L R 2008 J. Org. Chem. 73 3311; (c) Nagarathinam M and Vittal J J 2006 A rational approach to crosslinking of coordination polymers using the photochemical [2+2] cycloaddition reaction Macromol. Rapid Commun. 27 1091; (d) Nagarathinam M, Peedikakkal A M P and Vittal J J 2008 Stacking of double bonds for photochemical [2+2] cycloaddition reactions in the solid-state Chem. Commun. 42 5277; (e) Seidl P R and Dias J F 2005 In The Chemistry of Cyclobutane Z Rappoport and J F Liebman (Eds.) (Chichester, UK: John Wiley) p. 213

  2. (a) Schmidt G M J 1971 Photodimerization in the solid-state Pure Appl. Chem. 27 647; (b) Gautam R D and Kannan V 1986 What is the maximum yield in the solid state cinnamic acid dimerisation? A combinatorial mathematical approach J. Chem. Sci. 96 351; (c) Gopalan R S and Kulkarni G U 2001 An investigation of the photo-reactive and unreactive polymorphs of \(o\)-ethoxy cinnamic acid and of its photodimer J. Chem. Sci. 113 307

  3. (a) MacGillivray L R, Papaefstathiou G S, Friščić T, Hamilton T D, Bučar D -K, Chu Q, Varshney D B and Georgiev I G 2008 Supramolecular control of reactivity in the solid state: from templates to ladderanes to metal-organic frameworks Acc. Chem. Res. 41 280; (b) Georgiev I G and MacGillivray L R 2007 Metal-mediated reactivity in the organic solid state: from self-assembled complexes to metal-organic frameworks Chem. Soc. Rev. 36 1239; (c) Vittal J J 2007 Supramolecular structural transformations involving coordination polymers in the solid state Coord. Chem. Rev. 251 1781; (d) Kole G K and Vittal J J 2013 Solid-sate Reactivity and Structural Transformations Involing Coordination Polymers Chem. Soc. Rev. 42 1755; (e) Medishetty R, Park I, Lee S S and Vittal J J 2016 Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers Chem. Commun. 52 3989

  4. (a) Peedikakkal A M P, Peh C S Y, Koh L L and Vittal J J 2010 Metal-organic frameworks containing a tetrapyridylcyclobutane ligand derived from isomerization reaction Inorg. Chem. 49 6775; (b) Braga D, d’Agostino S and Grepioni F 2012 Co-Crystals and Salts Obtained from Dinitrogen Bases and 1,2,3,4-Cyclobutane Tetracarboxylic Acid and the Use of the Latter As a Template for Solid-State Photocyclization Reactions Cryst. Growth Des.  12 4880; (c) Pattabiraman M, Natarajan A, Kaliappan R, Mague J T and Ramamurthy V 2005 Template directed photodimerization of trans-1,2-bis(n-pyridyl)ethylenes and stilbazoles in water Chem. Commun. 36 4542

  5. (a) Dutta S, Bucar D –K, Elacqua E and MacGillivray L R 2013 Single-crystal-to-single-crystal direct cross-linking and photopolymerisation of discrete Ag(I) complex to give a 1D poly-cyclobutane coordination polymer Chem. Commun. 49 1064; (b) Chu Q, Swenson D C and MacGillivray L R 2005 Single-crystal-to-single-crystal transformation mediated by argentophilic forces converts a finite metal complex into an infinite coordination network Angew. Chem. Int. Ed. 44 3569; (c) Papaefstathiou G S, Zhong Z, Geng L and MacGillivray L R 2004 Coordination-driven self-assembly directs a single-crystal-to-single-crystal transformation that exhibits photocontrolled fluorescence J. Am. Chem. Soc. 126 9158; (d) Peedikakkal A M P, Koh L L and Vittal J J 2008 Photodimerization of a 1D hydrogen-bonded zwitter-ionic lead(II) complex and its isomerization in solution Chem. Commun. 441; (e) Peedikakkal A M P and Vittal J J 2008 Solid-State Photochemical [2+2] Cycloaddition in a Hydrogen-Bonded Metal Complex Containing Several Parallel and Crisscross C=C bonds Chem. –Eur. J.  14 5329; (f) Paul A K, Karthik R and Natarajan S 2011 Synthesis, structure, photochemical [2+2] cycloaddition, transformation, and photocatalytic studies in a family of inorganic-organic hybrid cadmium thiosulfate compounds Cryst. Growth Des. 11 5741; (g) Medishetty R, Husain A, Bai Z Z, Runčevski T, Dinnebier R E, Naumov P and Vittal J J 2014 Single crystals popping under UV light: a photosalient effect triggered by a [2+2] cyc-loaddition reaction Angew. Chem. Int. Ed. 53 5907; (h) Peedikakkal A M P 2017 Solid-state Photochemical [2+2] Cycloaddition Reaction of Hydrogen-Bonded Zn(II) Metal Complex Containing Several Parallel C=C Bonds J. Chem. Sci. 129 239

  6. (a) Mir M H, Koh L L, Tan G K and Vittal J J 2010 Single-crystal to single-crystal photochemical structural transformations of interpenetrated 3D coordination polymers by [2+2] cycloaddition reactions Angew. Chem. Int. Ed.  49 390; (b) Medishetty R, Koh L L, Kole G K and Vittal J J 2011 Solid-state structural transformations from 2D interdigitated layers to 3D interpenetrated structures Angew. Chem. Int. Ed. 50 10949

  7. Murthy G S, Arjunan P, Venkatesan K and Ramamurthy V 1987 Consequences of lattice relaxability in solid state photodimerizations Tetrahedron 43 1225

    Article  CAS  Google Scholar 

  8. (a) Kaupp G 2002 Solid-state reactions, dynamics in molecular crystals Curr. Opin. Solid State Mater. Sci. 6 131; (b) Kaupp G, Naimi-Jamal M R and Schmeyers J 2002 Quantitative reaction cascades of ninhydrin in the solid state Chem. Eur. J. 8 594; (c) Kaup G and Naimi-Jamal M R 2005 Mechanically induced molecular migrations in molecular crystals CrystEngComm 7 402

  9. (a) Harada J and Ogawa K 2009 Pedal Motion in Crystals Chem. Soc. Rev. 38 2244; (b) Harada J and Ogawa K 2001 Invisible but Common Motion in Organic Crystals? A Pedal Motion in Stilbenes and Azobenzenes J. Am. Chem. Soc. 123 10884; (c) Harada J and Ogawa K 2001 Ethane bond length in 1,2-diphenylethanes Struct. Chem. 12 243; (d) Harada J and Ogawa K 2004 X-ray Diffraction Analysis of Nonequilibrium States in Crystals? Observation of an Unstable Conformer in Flash-Cooled Crystals J. Am. Chem. Soc. 126 3539; (e) Harada J and Ogawa K 2014 What Molecules Are Likely or Unlikely To Undergo Pedal Motions in Crystals? Cryst. Growth. Des. 14 5182

  10. (a) Tanaka K, Hiratsuka T, Ohba S, Naimi-Jamal M R and Kaupp G 2003 Unidirectional cis-trans photoisomerization of cis-3,\(3^{\prime }\)-bis(diphenylhydroxymethyl)stilbene in inclusion complex crystals J. Phys. Org. Chem. 16 905; (b) Kaupp G, Schmeyers J and Hangen U D 2002 Anisotropic molecular movements in organic crystals by mechanical stress J. Phys. Org. Chem. 15 307; (c) Kaupp G, Schmeyers J, Kato M, Tanaka K and Toda F 2002 Space-demanding intramolecular isomerizations in the solid state J. Phys. Org. Chem. 15 148; (d) Kaupp G, Schmeyers J, Kato M, Tanaka K, Harada N and Toda F 2001 A non-topotactical thermal rearrangement without change of the macroscopic crystal shape J. Phys. Org. Chem. 14 444

  11. (a) Ohba S, Hosomi H and Ito Y 2001 In situ X-ray observation of pedal-like conformational change and dimerization of trans-cinnamamide in cocrystals with phthalic acid J. Am. Chem. Soc. 123 6349; (b) Natarajan A, Mague J T, Venkatesan K and Ramamurthy V 2005 Large molecular motions are tolerated in crystals of diamine double salt of trans-chlorocinnamic acids with trans-1, 2-diaminocyclohexane Org. Lett. 1895; (c) Furukawa D, Kobatake S and Matsumoto A 2008 Direct observation of change in the molecular structure of benzyl (Z,Z)-muconate during photoisomerization in the solid state Chem. Commun. 55; (d) Nishizawa N, Furukawa D, Kobatake S and Matsumoto A 2010 Crystal Phase Transition and Solid-State Photoisomerization of Benzyl (\(Z,Z\))-Muconate Polymorphs Studied by Direct Observation of Crystal Structure Change Cryst. Growth. Des. 10 3203; (e) Bhogala B R, Captain B, Parthasarathy A and Ramamurthy V 2010 Thiourea as a template for photodimerization of azastilbenes J. Am. Chem. Soc. 132 13434; (f) Elacqua E, Kaushik P, Groeneman R H, Sumrak J C, Bucar D -K and MacGillivray L R 2012 A supramolecular protecting group strategy introduced to the organic solid state: enhanced reactivity through molecular pedal motion Angew. Chem. Int. Ed.51 1037

  12. (a) Robert F, Naik A D, Tinant B, Robiette R and Garcia Y 2009 Insights into the origin of solid-state photochromism and thermochromism of N-salicylideneanils: the intriguing case of aminopyridines Chem. Eur. J. 15 4327; (b) Kochman M A, Bil A and Morrison C A 2013 Hybrid QM/QM simulations of photochemical reactions in the molecular crystal N-salicylidene-2-chloroaniline Phys. Chem. Chem. Phys. 15 10803

  13. Natarajan A, Mague J T, Venkatesan K, Arai T and Ramamurthy V 2006 Volume-demanding cis-trans isomerization of 1, 2-diaryl olefins in the solid state J. Org. Chem. 71 1055

    Article  CAS  Google Scholar 

  14. (a) Sinnwell M A, Ingenthron B J, Groeneman R H and MacGillivray L R 2016 Stereoselective and Quantitative [2+2] Photodimerization of a Symmetrical Octafluoro Stilbene in the Solid State: Face-to-Face Stacking of the Fluorinated Rings in trans-1,2-bis(2,3,5,6-tetrafluorophenyl)ethylene J. Fluor. Chem. 188 5; (b) Medishetty R, Bai Z Z, Yang H, Wong M W and Vittal J J 2015 Influence of Fluorine Substitution on the Unusual Solid-State [2 + 2] Photo-Cycloaddition Reaction between an Olefin and an Aromatic Ring Cryst. Growth. Des. 15 4055

  15. (a) Kole G K, Tan G K and Vittal J J 2011 Role of anions in the synthesis of cyclobutane derivatives via [2 + 2] cycloaddition reaction in the solid state and their isomerization in solution J. Org. Chem. 76 7860; (b) Kole G K, Tan G K and Vittal J J 2012 Solid state photodimerization of trans-2-(4-pyridyl)-4-vinylbenzoic acid via salt formation and isomerisation of cyclobutane compounds in solution CrystEngComm 14 7438

  16. (a) Hill Y and Briceño A 2007 Exploiting the use of hydrogen bonding and metal-coordination in the self-assembly of photoreactive multicomponent networks Chem. Commun. 3930; (b) Hill Y, Linares M and Briceño A 2012 Combining topochemical [2+2] photoreactions and hydrothermal isomerisation for the regioselective and quantitative preparation of rtct-pyridylcyclobutanes New J. Chem.  36 554; (c) Briceño A, Fulgence A, Hill Y and Atencio R 2008 A non-photochemical route for the regioselective preparation of rtct-pyridylcyclobutanes via hydrothermal isomerisation promoted by polymolybdates Dalton Trans. 3275

  17. (a) Horner M and Hünig S 1977 Bicyclo[1.1.0]butanes. A new synthetic route and valence isomerizations J. Am. Chem. Soc. 99 6120; (b) Horner M and Hünig S 1977 Reversible Transition between a [4]Radialene and a Cyclobutadiene by Electron Transfer Angew. Chem. Int. Ed. Engl. 16 410

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Acknowledgements

The author would like to acknowledge the support provided by the Deanship of Scientific Research (DSR) at King Fahd University of Petroleum and Minerals (KFUPM) for funding this work through Project No. IN131005. The author is grateful to Prof. J. J. Vittal (National University of Singapore), Dr. M. B. Fettouhi and Dr. T. F. Garrison (King Fahd University of Petroleum and Minerals) for helpful discussions.

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  1. Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran, 31261, Saudi Arabia

    Abdul Malik P Peedikakkal

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Correspondence to Abdul Malik P Peedikakkal.

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Peedikakkal, A.M.P. Solid state photodimerization in an organic salt of 1,2-bis(4-pyridyl)ethylene and trifluoromethane sulphonic acid via pedal-like motion. J Chem Sci 129, 733–739 (2017). https://doi.org/10.1007/s12039-017-1300-8

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