Journal of Photoscience

Korean Society of Photoscience (한국광과학회)
권호 표지

Weak Interactions Between Organic Molecules and Alkali Metal Ions Present in Zeolites Help Manipulate the Excited State Behavior of Organic Molecules

  • Ramamurthy, V. (Department of Chemistry, Tulane University)
  • Published : 2003.04.01
Download PDF
⟨ Previous Next ⟩

Abstract

Zeolite is a porous highly interactive matrix. Zeolitic cations help to generate triplets from molecules that possess poor intersystem crossing efficiency. Certain zeolites act as electron acceptors and thus can spontaneously generate radical cations. Zeolites also act as proton donors and thus yield carbocations without any additional reagents. These reactive species, radical cations and carbocations, have long lifetime within a zeolite and thus lend themselves to be handled as ‘regular’ chemicals. Internal structure of zeolites is studded with cations, the counter-ions of the anionic framework. The internal constrained structure and the cations serve as handles for chemists to control the behavior of guest molecules included within zeolites.

Keywords

References

  1. Tetrahedron Symposium in Pring #29, Tetrahedron v.43 Organic Chemistry in Anisotropic Media V.Ramamurthy,V.(ed.);J.R.Scheffer(ed.);N.J.Turro(ed.)
  2. Tetrahedron Symposium in Print #81, Tetrahedron v.56 Molecular Assembly and Reactivity of Organic Crystals and Related Structures M.Garcia-Garibay(ed.);V.Ramamurthy(ed.);J.R.Scheffer(ed.)
  3. Photochemistry in Organized and Constrained Media V.Ramamurthy(ed.)
  4. Introduction oto Zeolite Science and Practice Van-Bekkum,H,;E.M.Flanigen;J.C.Jansen
  5. An Introduction to Zeolite Molecular Sieves Dyer,A.
  6. Zeolite Molecular Sieves: Structure, Chemistry and Use Breck,D.W.
  7. Advanced Zeolite Science and Applications J.C.Jansen(ed.);M.Stocker(ed.);H.G.Karge(ed.);J.Weitkamp(ed.)
  8. Inclusion Chemistry with Zeolites: Nanoscopic Materials by Design N.Herron(ed.);D.R.Corbin(ed.)
  9. Acc. Chem. Res. v.26 Photochemistry in Organized and Confining Media: A Model Weiss,R.G.;V.Ramamurthy;G.S.Hammond
  10. Ad. Photochem. v.18 A Model for the Influence of Organized Media on Photochemical Reactions Ramamurthy,V.;R.G.Weiss;G.S.Hammond
  11. Angew. Chem. Int. Ed. Engl. v.14 The Photochemistry of Organic Solids Cohen,M.D.
  12. The Canadian Mineralogist v.18 no.2 The Canadian Mineralogist. POLYVOL Program Documentation
  13. Modern Molecular Photochemistry Turro.N.J.
  14. Luminescence of Liquids and Solids For a brief history P.Pringsheim;M.Vogel
  15. Handbook of Photochemistry(Second edition) Murov,S.L;I.Carmichael;G.L.Hug
  16. Phosphorimetry Hurtubise,R.J.
  17. Room Temperature Phosphorimetry for Chemical Analysis Vo-Dinh.T.
  18. J. Am. Chem. Soc. v.114 Heavy Atom Induced Phosphorescence of Aromatics and Olefins Included within Zeolites Ramamurthy,V.;J.V.Caspar;E.W.Kuo;D.R.Corbin;D.F.Eaton
  19. J Photochem Photobiol A: Chemistry v.50 Modification of photochemical reactivity by zeolites: Location of guests within faujasites by heavy atom induced phosphorescence Ramamurthy,V.;J.V.Caspar;D.R.Corbin;D.F.Eaton
  20. Coord. Chem. Rev. v.97 The location of guests within X-type faujasite zeolites via external heavy atom induced phosphorescence Caspar,J.V.;V.Ramamurthy;D.R.Corbin
  21. Tetrahedron Letters v.31 Modification of photochemical reactivity by zeolites: Heavy cation induced phosphorescence and entrapment of rotational conformers of trans-stilbene Ramamurthy,V.;J.V.Caspar;D.R.Corbin
  22. J. Phys. Chem. v.94 Triplet state photophysics of naphthalene and α,ω-diphenylpolyenes included in heavy cation exchanged zeolites Ramamurthy,V.;J.V.Caspar;D.R.Corbin;B.D.Schlyer;A.H.Maki
  23. Chem. Rev. v.66 The triplet state and Molecular Electronic Processes in Organic Molecules Lower,S.K.;M. El Sayed
  24. J. Am. Chem. Soc. v.122 Heavy-Cation-Induced Phosphorescence of Alkanones and Azoalkanes In Zeolites As Hosts: Induced S₁ to T₁ (nπ$^*$) Intersystem Crossing and S$_0$ to T₁(nπ$^*$) Absorption Uppili,S.;V.Marti;A.Nikolaus;W.Adam;P.S.Engel;N.J.Turro;V.Ramamurthy
  25. Acc. Chem. Res. v.31 Observation of Radical Ions by Swiftness or Stealth Werst,D.W.;A.D.Trifunac
  26. J. Am. Chem. Soc. v.113 Preparation and spectroscopic characterization of polarons and bipolarons of thiophene oligomers within the channels of pentasil zeolites: The evolution of organic radical ions into conducting polymers Caspar,J.V.;V.Ramamurthy;D.R.Corbin
  27. J. Am. Chem. Soc. v.113 Generation, entrapment and spectroscopic characterization of radical cations of α,ω-diphenylpolyenes within the channels of pentasil zeolites Ramamurthy,V.;J.V.Caspar;D.R.Corbin
  28. Chimia v.46 Photochemistry and Photophysics within Zeolites Ramamurthy,V.
  29. Acc Chem Res. v.25 Photochemistry and Photophysics of Organic Molecules Included within Zeolites Ramamurthy,V.;D.F.Eaton;J.V.Caspar
  30. J. Chem. Soc. Chem. Commun. Exceptionally Stable Carbocation from Indene Generated and Trapped within Ca Y Zeolite Pitchumani,K.;V.Ramamurthy
  31. J. Chem. Soc. Chem. Commun. Generation of Stable and Persistent Carbocations From 4-Vinylanisole Within Zeolites Jayathirtha Rao, V.;N.Prevost;V.Ramamurthy;M.Kojima;L.J.Johnston
  32. J. Chem. Soc. Chem. Commun. Pitchumani,K.;P.H.Lakshminarasimhan;N.Prevost;D.R.Corbin;V.Ramamurthy
  33. J. Chem. Soc. Chem. Commun. Zeolite as a Reagent and as a Catalyst: Reduction and Isomerization of Stilbenes by CaY Pitchumani,K.;A.Joy;N.Prevost;V.Ramamurthy
  34. Tetrahedron Letters v.38 Cation Radical and Carbocation Mediated Reactions within CaY Zeolite: 1-Phenyl 3,4-dihydronaphthalene Pitchumani,K.;P.H.Lakshminarasimhan;G.Turner;M.G.Bakker;V.Ramamurthy
  35. J. Am. Chem. Soc. v.118 Electron Transfer Reactions within Zeolites: Radical Cations from Benzonorbornadiene and Dibenzobarrelene Pitchumani,K.;D.R.Corbin;V.Ramamurthy
  36. J. Chem. Soc. Chem. Commun. Energy Transfer, Proton Transfer and Electron Transfer Reactions Within Zeolites Ramamurthy,V.;P.H.Lakshminarasimhan;C.P.Grey;L.J.Johnston
  37. J. Phys. Chem. B. v.103 Characterization of persistnt intermediates generated upon inclustion of 1,1-diarylethylenes within CaY: Spectroscopy and Product Studies Lakshminarasimhan,P.H.;K.J.Thomas;L.Brancaleon;P.D.Wood;L.J.Johnston;V.Ramamurthy
  38. J. Am. Chem. Soc. v.120 Facial Selective Photoreduction of Steroids: Role of Zeolites Jayathirtha Rao, V.;S.Uppili;D.R.Corbin;S.Schwarz;S.R.Lustig;V.Ramamurthy
  39. Tetrahedron Letters v.42 Controlling the Reactive State Through Cation Binding: Photochemistry of Enones within Zeolites Uppili,S.;S.Takagi;R.B.Sunoj;P.H.Lakshminarasimhan;J.Chandrasekhar;V.Ramamurthy
  40. J. Comput. Chem. v.22 Configuration Interaction and Density Functional Study of the Influence of Lithium Cation Complexation on Vertical and Adiabatic Excitation Energies of Enones Sunoj,R.B.;P.H.Lakshminarasimhan;V.Ramamurthy;J.Chandrasekhar
  41. Langmuir v.16 Probing zeolites with organic molecules: Supercages of X and Y zeolites are superpolar Uppili,S.;K.J.Thoms;E.Crompton;V.Ramamurthy
  42. J. Am. Chem. Soc. v.118 Selective Oxidation of Olefins within Organic Cation Exchanged Zeolites Li,X.;V.Ramamurthy
  43. J. Chem. Soc. Chem. Commun. Generation and Reactivity of Singlet Oxygen Within Zeolites: Remarkable Control of hydroperoxidation of alkenes Robbins,R.;V.Ramamurthy
  44. Tetrahedron v.56 Singlet Oxygen Mediated Oxidation of Olefins Within Zeolites: Selectivity and Complexities Shailaja,J.;J.Sivaguru;R.J.Robbins;V.Ramamurthy;R.B.Sunoj;J.Chandrasekhar
  45. J. Am. Chem. Soc. v.118 Remarkable Product Selectivity During Photo-Fries and Photo-Claisen Rearrnagements within Zeolites Pitchumani,K.;M.Warrier;V.Ramamurthy
  46. Tetrahedron Letters v.37 Photo-Fries Reaction of Naphthyl Esters within Zeolites Pitchumani,K.;M.Warrier;C.Cui;R.G.Weiss;V.Ramamurthy
  47. Re. Chem. Intermediates v.25 Utility of zeolitic medium in photo-Fries and photo-Claisen rearrangements Pitchumani,K.;M.Warrier;V.Ramamurthy
  48. J. Am. Chem. Soc. v.121 Photo-Fries reactions of 1-naphthyl esters in cation exchanged zeolite Y and polythylene media Gu,W.;M.Warrier;V.Ramamurthy;R.G.Weiss
  49. Spectrum v.12 no.3 Enforcing molecules to behave Joy,A.;M.Warrier;V.Ramamurthy
  50. Langmuir v.16 Understanding the Influence of Active (Zeolite) and Passive (Polyethylene) Reaction Cages on Photo-Claisen Rearrangements of Aryl Benzyl Ethers Gu,W.;M.Warrier;B.Schoon;V.Ramamurthy;R.G.Weiss
  51. J. Am. Chem. Soc. v.122 Cation-π Interaction Controlled One-Way Geometric Photoisomerization of Diphenyl-cyclopropane Lakshminarasimhan,P.H.;R.B.Sunoj;J.Chandrasekhar;V.Ramamurthy
  52. Tetrahedron Letters Asymmetrically Modified Zeolite As a Medium For Enantioselective Photoreactions: Reactions From Spin Forbidden Excited States Joy,A.;R.J.Robbins;K.Pitchumani;V.Ramamurthy
  53. J. Chem. Soc Chem. Comm. Zeolite as a host for chiral induction Sundarababu,G.;M.Leibovitch;D.R.Corbin;J.R.Scheffer;V.Ramamurthy
  54. J. Am. Chem. Soc. v.118 Asymmetric Induction in Photochemical Reactions Conducted in Zeolites and in the Crystalline State Leibovitch,M.;G.Olovsson;G.Sundarababu;V.Ramamurthy;J.R.Scheffer;J.Trotter
  55. J. Chem. Soc. Chem. Commun. Enantio Selective Photocyclization within Zeolites: Tropolone methyl ether in Chirally Modified Zeolites Joy,A.;J.R.Scheffer,D.;R.Corbin;V.Ramamurthy
  56. Proceedings of 12$^{th}$ International Zeolite Conference Studies on Chiral Induction within Zeolites: Photoelectrocyclization of Tropolone alkylethers Joy,A.;D.R.Corbin;V.Ramamurthy;M.M.J.Traecy(ed.);B.K.Marcus(ed.);B.E.Bisher(ed.);J.B.Higgins(ed.)
  57. Chemistry Eur J. v.6 Chiral photochemistry within zeolites Joy,A.;V.Ramamurthy
  58. J. Am. Chem. Soc. v.122 Photochemistry of Tropolone ethers and 2,2-dimethyl-1-(2H)-naphthalenones Within a Zeolite: Chiral Amplification Via Confinement Joy,A.;S.Uppili;M.R.Netherton;J.R.Scheffer;V.Ramamurthy
  59. Org. Letters v.2 Chirally Modified Zeolite as a Reaction Medium: Photochemistry of an Achiral Tropolone ether Joy,A.;J.R.Scheffer;V.Ramamurthy
  60. Org. Letters v.2 Enantioselective Photoreduction of arylalkyl ketones via restricting the reaction to chirally modified zeolites Shailaja,J.;K.J.Ponchot;V.Ramamurthy
  61. Org Letters v.2 Enantio- and diastereo-differentiating cis, trans-photoisomerization of 2β,3β-diphenylcyclopropane-1α-carboxylic acid derivatives in organized media Cheung,E.;K.C.W.Chong;S.Jayaraman;V.Ramamurthy;J.R.Scheffer;J.Trotter
  62. Tetrahedron Letters v.41 Influence Of Chiral Auxiliaries Is Enhanced Within Zeolites Jayaraman,S.;S.Uppili;A.Natarajan;A.Joy;K.C.W.Chong;M.R.Netherton;A.Zenova;J.R.Scheffer;V.Ramamurthy
  63. Microporous and Mesoporous Materials v.48 Use of a Confined Space (Zeolite) in Enatio and Distereoselective Photoreactions Shailaja,J.;J.Sivaguru;S.Uppili;A.Joy;V.Ramamurthy
  64. Organic Solid State Reactions Achieving Enantio and Diastereoselectivities in Photoreactions Throught the Use of a Confined Space Sivaguru,J.;J.Shailaja;S.Uppili;K.Ponshot;A.Joy;N.Arunkumar;V.Ramamurthy;F.Toda(ed.)
  65. J. Am. Chem. Soc. v.124 Use of Chirally Modified Zeolites and Crystals in Photochemical Asymmetric Synthesis Chong,K.C.W.;S.Jayaraman;T.Shichi;Y.Yoshimi;V.Ramamurthy;J.R.Scheffer
  66. Org Letters v.4 Enhanced Enantio-and Diastereoselectivities via Confinement: Photorearrangement of 2,4-Cyclohexadienones Included in Zeolites Uppili,S.;V.Ramamurthy
  67. J. Chem. Soc. Chem. Commu. Confined Space and Cations Enhance the Power of a Chiral Auxiliary: Photochemistry of 1,2-Diphenylecyclopropane Derivatives Sivaguru,J.;J.R.Scheffer;V.Ramamurthy
  68. Org Letters v.4 Control of Enantioselectivity in the Photochemical Conversion of α-Oxoamides into β-Lactam Derivatives Arunkumar,N.;K.Wang;V.Ramamurthy;J.R.Scheffer