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Solid-state Photochemical [2+2] Cycloaddition Reaction of Hydrogen-Bonded Zn(II) Metal Complex Containing Several Parallel C=C Bonds

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Abstract

A 2D hydrogen-bonded dinuclear Zn(II) complex, [{Zn(H2O)3(bpe)2}2(bpe)](NO3)4⋅3bpe ⋅14H2O, 1 (bpe = 4,4′-bipyridylethylene) containing coordination complex cations, [{Zn(H2O)3(bpe)2}2(μ-bpe)] 4+ and free bpe and lattice water molecules shows face-to-face, ππ stacking of two of the four free bpe molecules with coordinated bpe ligands. Out of eight bpe molecules, six are aligned in parallel fashion with short C ⋯C distances of 3.663–3.814 Å and they undergo photochemical [2 + 2] cycloaddition reaction. The photoreaction conducted on ground sample of 1 in the solid-state affords rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) product in 75% yield. The molecular movement of free bpe molecules was tested by conducting the photoreaction in ground sample and heated sample of single crystals. The photoreactivity study of 1 indicates that the free bpe molecules are locked between the cationic [{Zn(H2O)3(bpe)2}2(bpe)] 4+ layers.

Single crystals of 2D hydrogen-bonded dinuclear Zn(II) complex of 4,4′-bipyridylethylene (bpe) containing coordination complex cation and free non-coordinated bpe molecules undergo photochemical [2+2] cycloaddition reaction via molecular movement which is accelerated by mechanical grinding.

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References

  1. (a) Vittal J J 2007 Supramolecular structural transformations involving coordination polymers in the solid state Coord. Chem. Rev. 251 1781; (b) Medishetty R and Vittal J J 2014 Metal-Organic Frameworks for Photochemical Reactions Struct. Bond. 157 105

  2. 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

    Article  CAS  Google Scholar 

  3. 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

    Article  CAS  Google Scholar 

  4. (a) 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; (b) Medishetty R, Tandiana R, Wu J, Bai Z, Du Y and Vittal J J 2015 A step-by-step Assembly of a 3D Coordination Polymer in the Solid-state by Desolvation and [2 + 2] Cycloaddition Reactions Chem.–Eur. J. 21 11948; (c) Kole G K, Peedikakkal A M P, Toh B M F and Vittal J J 2013 Solid-State Structural Transformations and Photoreactivity of 1D-Ladder Coordination Polymers of Pb II Chem.–Eur. J. 19 3962

  5. (a) 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; (b) Kole G K and Vittal J J 2013 Solid-sate Reactivity and Structural Transformations Involing Coordination Polymers Chem. Soc. Rev. 42 1755

  6. (a) Peedikakkal A M P and Vittal J J 2008 Chem.–Eur. J. 14 5329; (b) Medishetty R, Tandiana R and Vittal J J 2014 Stepwise Host–Guest [2 + 2] Photoreaction in a Hydrogen-Bonded One-Dimensional Coordination Polymer to a Two-Dimensional Layered Structure Cryst. Growth. Des. 14 3186

  7. (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 aciddimerisation? A combinatorial mathematical approach J. Chem. Sci. 96 351; (c) Gopalan R S and Kulakarni 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

  8. 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 

  9. Kaup G and Naimi-Jamal M R 2005 Mechanically induced molecular migrations in molecular crystals CrystEngComm 7 402

    Article  Google Scholar 

  10. (a) Harada J and Ogawa K 2014 What Molecules Are Likely or Unlikely To Undergo Pedal Motions in Crystals? Cryst. Growth. Des. 14 5182; (b) Harada J and Ogawa K 2009 Pedal Motion in Crystals Chem. Soc. Rev. 38 2244; (c) 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; (d) Chu Q, Swenson D C and MacGillivray L R 2005 A 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

  11. 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. 7 1895

    Article  CAS  Google Scholar 

  12. Lee J Y, Hong S J, Kim C and Kim Y 2005 Construction of an interpenetrated 3-D network by [2 + 2] cycloaddition of Zn(ClO4)2 and 1,2-trans-(4-pyridyl)ethene: Counter anion effects Dalton Trans. 3716

  13. Ramamurthy V and Venkatesan K 1987 Photochemical reactions of organic crystals Chem. Rev. 87 433

    Article  CAS  Google Scholar 

  14. Sokolov A N, Swenson D C and MacGillivray L R 2008 Conformational polymorphism in a heteromolecular single crystal leads to concerted movement akin to collective rack-and-pinion gears at the molecular level Proc. Natl. Acad. Sci. USA 105 1794

    Article  CAS  Google Scholar 

  15. Braga D and Grepioni F 2004 Reactions between or within molecular crystals Angew. Chem. Int. Ed. 43 4002

    Article  CAS  Google Scholar 

  16. Boldyrev V V 2004 Mechanochemical modification and synthesis of drugs J. Mater. Sci. 39 5117

    Article  CAS  Google Scholar 

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Acknowledgments

The author would like to acknowledge the support provided by the Deanship of Scientific Research (DSR) at King Fahd University of Petroleum & Minerals (KFUPM) for funding this work through project No. IN131005. The author is grateful to Prof. Jagadese J. Vittal, National University of Singapore for helpful discussion on the manuscript.

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Correspondence to ABDUL MALIK P PEEDIKAKKAL.

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Supplementary Information (SI)

All additional information pertaining to the characterization of photoreacted 1 under various conditions using 1H NMR, product distribution, TGA, and crystallographic data of 1 are given in the Supporting Information available at www.ias.ac.in/chemsci.

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PEEDIKAKKAL, A.M.P. Solid-state Photochemical [2+2] Cycloaddition Reaction of Hydrogen-Bonded Zn(II) Metal Complex Containing Several Parallel C=C Bonds. J Chem Sci 129, 239–247 (2017). https://doi.org/10.1007/s12039-016-1218-6

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