Professor Jagadese J, VITTAL

B.Sc., 1975, University of Madras; M.Sc., 1977, Madurai University; Ph.D., 1982, I. I. Sc. Bangalore

Contact Information

Department of Chemistry, NUS 
3 Science Drive 3 
Singapore 117543 
Office: S8-05-07
Tel: (65)-6516-2975
Fax: (65)-6779-1691
Email: chmjjv@nus.edu.sg


Research Interests

Crystal Engineering & Inorganic Materials


(A) Crystal Engineering: Current research activities in our group includes rational design of metal coordination polymers with multi-dimensional network structures using a number of linear and angular spacer ligands. In this exploratory research we systematically study the properties of supramolecular building blocks such as shape, size and directionality of the functional groups to understand how these parameters control and influence the crystal packing and hence the supramolecular structures. Photoreactive coordination polymers, and porous materials for gas storage properties are our being investigated. Some of the recent results are presented below.

Solid State Reactivity and [2+2] Cycloaddition Reactions: We are now investigating photochemical [2+2] cycloaddition reactions in organic salts, co-crystals, metal complexes, coordination polymers (SPs) and metal-organic frameworks (MOFs). We have shown that it is possible to design photoreactive CPs and MOFs and conduct single-crystal-to-single-crystal (SCSC) reactions with ease than ever before. We have used this photodimerization reaction as a tool to follow the structural transformations and post-synthetically modify the pillar ligands in MOFs. Usually MOFs are made in a single-step by self-assembly method. There are different approaches available to make them in steps, i.e., non-self-assembly methods. In our laboratory, we employ a combination of desolvation and [2+2] cycloaddition reaction to convert 1D CPs to 2D CPs and then to 3D CPs (MOFs) in a step-by-step manner. This gives full synthetic control on the nature of MOFs obtained.

Figures: Structural transformation from a 2D CP to a 3D CP by [2+2] cycloaddition reaction (above). The modification of pillar ligand in a MOF by SCSC Photochemical Structural Transformations (below).

You can be recycled Mr. C-C BOND!: Although the solid state [2+2] cycloaddition reactions gained popularity in CPs and MOFs, the reverse reaction of cleaving the cyclobutane rings to olefins has not been explored at all. This property can be effectively used for some potential applications such as applications in photonic devices, sensor techniques, lithographic patterning, imaging techniques, data processing and data storage. Of late we found the potassium trans-4,4'-stilbenedicarboxylate shows reversibility during the UV light driven [2+2] cycloaddition reaction and the thermal cleavage of resultant cyclobutane ring. Surprisingly the single crystals were retained during these the reversible reactions. More interestingly these compounds show different emissive properties during this reversible structural transformation. This transformation is accompanied by the loss of luminescence as shown below. This is in collaboration with Prof Masaki Kawano, POSTECH, Korea.

 

Figures: Reversible formation and cleavage of cyclobutane ring in cycles (left) and the changes in the photoluminescence properties (right).

MOF-COF Hybrid Structures:The photochemical [2+2] cycloaddition reaction has been employed to carry out the polymerization of the conjugated diene ligand, bpeb. Several 3D structures incorporating organic polymer comprising cyclobutane rings and coordination polymers have been obtained in SCSC manner. Monocrystalline metal complexes of organic polymer ligands are hitherto unknown. In one case the organic polymer can be depolymerized by the cleavage of cyclobutane rings in an SCSC manner. This is a collaborative efforts with Prof. Shim Sung Lee, Gyeongsang National University, Jinju, Korea.

Figures: Formation of organic ligand by [2+2] cycloaddition reactions inside CPs and MOFs forming coordination polymer-organic polymer hybrid structures.

Photoactuating Materials:A visually impressive dynamic behavior of single crystals of three Zn(II) complexes which are self-propelled under UV light has been investigated with our collaboration with Prof. Pance Naumov, New York University, Abu Dhabi.  This photosalient effect is a consequence of accumulation and sudden release of a strain created by crystal expansion following the formation of 1D coordination polymers by [2+2] cycloaddition reaction. Understanding of this effect, which is mechanistically analogous to the bursting of popcorn in a hot pan, could aid to harness light energy and convert it into kinetic energy in the new light-driven mechanical actuators. Here our aim is to design a reversible photosalient materials that can be reused.

Figures: A schematic diagram showing the popping effect of UV light on the single crystals (left) and different types of mechanical behavior of these crystals (right)


(B) Nanoscale Materials: The study of nanometer size compounds is an exciting area of research which offers opportunities for innovation and creativity.

Nanoscale materials exhibit quantum behavior due to their size and are promising materials for new technologies. Our research focuses on the synthesis of nanoscale metal chalcogenide materials and the characterization of their properties. The chemical, physical, electronic, optical, magnetic and catalytic properties of nanocrystals depend on the size and shape of the nanomaterials. However synthesis of stable monodispersed nanocrystals is a real challenge in nanoscience. Currently we are also interested in developing solar cells.

Single Molecular Precursor Chemistry: We have been interested in developing the chemistry of transition and main group metal compounds with chalcogen containing ligands, RC{O}E-, RE-, R2NCS2 = (where E = S, Se and Te), dithioacetylacetonato and related ligands. We have shown that many of these compounds can be used as precursors to metal chalcogenides (as amorphous or crystalline powders, films and nanoparticles). Currently we are interested in the Group 6, 11, 12, 13, 14, transition and lanthanide metals. We have also developed single precursor routes to synthesize highly monodispersed nanoparticles of ME (M = Zn, Cd, Hg & Pb),  M2E (M = Cu & Ag), M2E3 (M = As, Sb & Bi), AME2 (A = Cu, Ag; M = Ga & In), where E = S, Se & Te,  etc.

 
  (a)       (b)  

Figures: (a) The formation of different size and shapes of Ag2Se nanocrystals from the precursor [(Ph3P)3Ag2(SeC{O}Ph)2]. (b) The toluene-soluble AgInS2 obtained from [(Ph3P)2AgIn(SeC{O}Ph)4] exhibits NLO properties.

Battery Materials: A wide range of materials have been considered as energy storage materials; of these Li ion battery is a promising one and of late this is one of the hottest areas of research due to recent oil crisis. We entered this field by accident when reported single-molecular precursor route to LiMO2 battery materials. The compounds [Li(H2O)M(N2H3CO2)3].H2O (M = Ni, Co) on pyrolysis yield LiNiO2 and LiCoO2 at 700oC in oxygen atmosphere and at T > 700oC in air. Currently we are collaborating with Physics and Chemical Engineering colleagues in developing LiFePO4 battery materials. We synthesized LiFePO4 nanoplates with uniform coating of 5 nm thick amorphous carbon layer by solvothermal method. The thickness along b-axis is found to be 30-40 nm, and such morphology favors a shorter diffusion length for Li+ ions, while exterior conductive carbon decoration provides connectivity for facile electron diffusion, resulting in high rate performances close to theoretical value, shown below. We also filed a US Patent on this material.

Figures: (Left) Galvanostatic charge - discharge cycle curves for LiFePO4C and (right) Capacity vs. Cycle number plots of LiFePO4/C nanoplates at various current rates 0.1 to 30 C


Cover pages


Textbook, 2011

Book, 2010

Book, 2006

Front Cover, 2005

Back Cover, 2006

Front Cover, 2006

Front Cover, 2006

Inside Cover, 2007

Front Cover, 2008

Inside Cover, 2008

Front Cover, 2008

Inside Cover, 2009

Cover, 2009


Frontispiece 2014


Back Cover 2014


Cover 2014

   

JJVittal’s full list of publications

JJVittal’s full CV


Representative Publications

Citations: About 16,500 citations from 480 publications & h-index - 65 (Google Scholar, Dec. 2016).

Books:

  1. G.R. Desiraju, J.J.Vittal and A. Ramanan, Crystal Engineering - A Texbook, World Scientific, 2011.

  2. E.R.T. Tiekink, J.J. Vittal and M.J. Zaworotko (Book Editors), Organic Crystal Engineering: Frontiers in Crystal Engineering, ISBN: 978-0-470-31990-1, Wiley, 2010

  3. E.R.T. Tiekink and J.J. Vittal (Book Editors), Frontiers in Crystal Engineering, ISBN: 0-470-02258-2, Wiley, 2006.


Reviews and Perspectives:

  1. R. Medishetty, I.H. Park, S.S. Lee and JJ Vittal, “Solid-state polymerization via [2+2] cycloaddition reaction involving coordination polymers”, Chem. Commun. 51(21) (2016) 3989 (Feature article)

  2. R. Medishetty, J. J. Vittal, “Metal-organic frameworks for photochemical reactions”, in Metal-organic frameworks for photonics applications (Editors: B. Chen and G. Qian), Struct. & Bond. 157 (2014) 105.

  3. A. Chanthapally, J. J. Vittal, ‘Metal-Organic Frameworks: Photoreactive Frameworks’, in the book Metal-Organic Framework Materials” (Editors: Leonard R. MacGillivray and Charles M. Lukehart), John Wiley & Sons, Ltd: Chichester, UK, pp. 135, 2014.

  4. G.K. Kole, J.J. Vittal, “Solid state reactivity, structural transformations involving coordination polymers,” Chem. Soc. Rev., 42(4) (2013) 1755 (invited review for the Werner issue)

  5. W.L. Leong and J.J. Vittal, "One-dimensional coordination polymers: Complexity and diversity in structures, properties, and applications", Chem. Rev. 111(2), (2010) 688.

  6. K. Biradha, C.-Y. Su, J.J. Vittal, “Recent Developments in Crystal Engineering,” Cryst. Growth & Des., 11(4) (2011) 875 (one of the most read articles in 2011)

  7. K. Biradha, A. Ramanan & J.J. Vittal, “Coordination Polymers versus Metal Organic Frameworks,” Cryst. Growth & Des., 9(7) (2009) 2969

  8. M. Nagarathinam, A.M.P. Peedikakkal and J.J. Vittal, "Stacking of double bonds for photochemical [2+2] cycloaddition reactions in the solid-state" Chem. Commun., (42) (2008) 5277 (invited feature article)

  9. J.J. Vittal and M.T. Ng, "Chemistry of Metal Thio- and Selenocarboxylates - Precursors for Metal Sulfide/Selenide Materials", Thin Films and Nanocrystals, Acc. Chem. Res., 39 (2006) 869. (invited review and cover page & one of the most-accessed articles in October-November, 2006).

  10. M. Nagarathinam and J.J. Vittal, "A rational approach to cross-linking of coordination polymers by photochemical [2+2] cycloaddition reaction", Macromol. Rapid Commun., 27 (2006) 1091. (invited feature article & back cover page).

  11. J.J. Vittal, "Supramolecular structural transformations involving coordination polymers in the solid state", Coord. Chem. Rev. 251 (2007), 1781. (invited review) (Highly cited paper by Thomson's Essential Science Indicators 2008-2010)

  12. R. Ganguly, B. Sreenivasulu and J.J. Vittal,"Amino acid containing reduced Schiff base as the building blocks for supramolecular structures" Coord. Chem. Revs. 252(8-9) (2008) 1027
    (invited & one of the top 25 hottest articles, April-June, 2008 )


Research Papers:

  1. C. E. Mulijanto, H. S. Quah, Geok Kheng Tan, B. Donnadieu, J.J. Vittal, “Curved crystal morphology, photoreactivity and photosalient behaviour of mononuclear Zn(II) complexes” IUCrJ,  4(1) (2017) 65

  2. M. Liu, H.S. Quah, S. Wen, Z. Yu, J.J. Vittal, W. Ji, “Efficient Third Harmonic Generation in a Metal-Organic Framework Compound” Chem. Mater., 28(10) (2016) 3385

  3. A. S. Hameed, M. V. Reddy, M. Nagarathinam, T. Runčevski, R.E Dinnebier, S. Adams, B. V. R. Chowdari and J. J. Vittal, “Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries,” Sci. Reports., 5 (2015) 16270

  4. R. Medishetty, R. Tandiana, J. Wu, Z. Bai, Y. Du, J.J. Vittal, “A Step-by-step Assembly of a 3D Coordination Polymer in the Solid State by desolvation and [2+2] Cycloaddition Reaction,” Chem. Eur. J., 21(34) (2015) 11948 (Hot Paper & Frontispiece) 

  5. H.S. Quah, W. Chen, M. K. Schreyer, H. Yang, M.W. Wong, J.J. Vittal, “Multiphoton Harvesting Metal Organic Frameworks,” by Nat. Commun., 6 (2015) 7954

  6. I.-H. Park, R. Medishetty, H.-H. Lee, C. E. Mulijanto, H. S. Quah, S. S. Lee, J.J. Vittal, “Formation of a Syndiotactic Organic Polymer inside a MOF via [2+2] Photo-Polymerization Reaction,” Angew. Chem. Int. Ed., 54(25) (2015) 7313

  7. V. Nalla, R. Medishetty, W. Yue, Z. Bai, S. Handong, W. Ji, J. J. Vittal, “Second harmonic generation from the “centrosymmetric” crystals,’ IUCrJ,  2 (2015) 317

  8. R. Medishetty, S. K. Sahoo, C. E. Mulijanto, P. Naumov, J.J. Vittal, “Photosalient behavior of photoreactivity crystals,” Chem. Mater., 27(5) (2015) 1821

  9. R. Medishetty, A. Husain, Z. Bai, T. Runčevski, R. Dinnebier, P. Naumov, J. J. Vittal, “Popping Single Crystals Under UV Light: The First Example of a Photosalient Effect Triggered by a [2+2] Cycloaddition Reaction,” Angew. Chem. Int. Ed., 53(23) (2014) 5907 (Hot paper & Cover page)

  10. I. H. Park, R. Medishetty, S.S. Lee, J.J. Vittal, “Solid-State Polymerization in a Polyrotaxane Coordination Polymer via [2+2] Cycloaddition Reaction,” Chem. Commun., 50(5) (2014) 6585

  11. I.H. Park, R. Medishetty, J.-Y. Kim, S.S. Lee, JJ Vittal, “Distortional Supramolecular Isomers of Polyrotaxane Coordination Polymers: Photoreactivity and Sensing of Nitro Compounds,” Angew. Chem. Int. Ed., 53(22) (2014) 5591

  12. S. K. Elsaidi, M. H. Mohamed, L. Wojtas, A.Chanthapally, T. Pham, B. Space, J. J. Vittal, M. J. Zaworotko, “Putting the Squeeze on CH4 and CO2 through Control over Interpenetration in Diamondoid Nets,” J. Am. Chem. Soc., 136(13) (2014) 5072

  13. I.-H. Park, A. Chanthapally, H.-H. Lee, H. S. Quah, S. S. Lee, J. J. Vittal, “Solid-State Conversion of a MOF to a Metal-Organo Polymeric Framework (MOPF) via [2+2] Cycloaddition Reaction,” Chem. Commun., 50(28) (2014), 3665 (inside cover)

  14. G.K. Kole, T. Kojima, M. Kawano, J.J. Vittal, “Reversible Single-Crystal-to-Single-Crystal Photochemical Formation and Thermal Cleavage of a Cyclobutane Ring,” Angew. Chem. Int. Ed., 53(8)(2014) 2143

  15. I.H. Park, A. Chanthapalli, Z. Zhang, S.S. Lee, M.J. Zaworotko, J.J. Vittal, "Metal-Organic Organo-Polymeric Hybrid Framework Reversible [2+2] Cycloaddition Reaction," Angew. Chem. Int. Ed., 53(2) (2014) 414 (Frontispiece)

  16. R. Medishetty, R. Tandiana, L. L. Koh, J.J. Vittal, “Assembly of 3D Coordination Polymers from 2D Sheets [2+2] Cycloaddition Reaction,” Chem. – A Eur. J., 20(5) (2014) 1231

  17. A. Chanthapally, W.T. Oh, J.J. Vittal, “Photoreactivity of Polymorphs of a Ladder Polymer with Crisscross, Parallel Orientations of C=C Bonds,” Chem. Commun., 50(4) (2014) 451

  18. R. Medishetty, T. T. S. Yap, L. L. Koh, J.J. Vittal, “Thermally Reversible Single-Crystal to Single-Crystal Transformation of  mononuclear to Dinuclear Zn(II) Complexes [2+2] Cycloaddition Reaction,” Chem. Commun., 49(83) (2013) 9567

  19. G.K. Kole, R. Medishetty, L.L. Koh, J.J. Vittal, “Influence of C-H•••p interaction on the solid–state [2+2] cycloaddition reaction of a Ag(I) coordination complex in an inorganic co-crystal,” Chem. Commun., 49 (56) 2013) 6298

  20. G. K. Kole, A.M.P. Peedikakkal, B.M.F. Toh, J.J. Vittal, “Solid State Structural Transformation, Photoreactivity of 1D Ladder Coordination Polymers of Pb(II),” Chem. – A Eur. J., 19(12) (2013) 3962 (Back cover page)

  21. I.-H. Park, S. S. Lee J. J. Vittal, “Guest-Triggered Supramolecular Isomerism in a Pillared-Layer Structure with Unusual Isomers of Paddle-Wheel by SBU Reversible Single-Crystal to Single-Crystal Transformation,” Chem. – A Eur. J., 19(8) (2013) 2695

  22. M. Nagarathinam, K.Saravanan, J.H. Phua, M. V. Reddy, B. V. R. Chowdari, J. J. Vittal,  “Redox Active Hybrid Metal Centered Oxalato Phosphate Open Framework 4 V Cathode Materials for Lithium Ion Batteries,” Angew. Chem. Int. Ed., 51 (2012) 5866

  23. A. Chanthapally, G.K. Kole, K. Qian, G.K. Tan, S. Gao, J.J. Vittal, “Thermal Cleavage of Cyclobutane Rings in the Photodimerized Coordination Polymeric Sheets”, Chem. – A Eur. J., 18(25) (2012) 7869

  24. M.  Nagarathinam, A. Chanthapally, S. H. Lapidus, P. W. Stephens, J. J. Vittal, “Mechanochemical Reactions of Coordination Polymers by Grinding with KBr” Chem. Commun., 48(20) (2012) 2585

  25. M.H. Mir, J.X. Ong, G.K. Kole, G.K. Tan, M.J. McGlinchey, Y. Wu, J. J. Vittal, “Photoreactive Gold(I) Macrocycles with Diphosphine, trans, trans- Muconate Ligands," Chem. Commun., 47(42) (2011) 11633

  26. R. Medishetty, L.L. Koh, G.K. Kole and J.J. Vittal, " Solid State Structural Transformation from 2D-Interdigitated Layer to 3D-Interpenetrated Structure", Angew. Chem., 50(46) (2011) 10949

  27. M.H. Mir, J.X. Ong, G.K. Kole, G.K. Tan, M.J. McGlinchey, Y. Wu and J.J. Vittal, "PHOTOREACTIVE Gold(I) Macrocycles with Diphosphine and trans, trans- Muconate Ligands", Chem. Commun., 47(42)(2011) 11633

  28. G.K. Kole, L.L. Koh, S.Y. Lee, S.S. Lee, and J.J. Vittal, “A new ligand for metal-organic framework and co-crystal synthesis: Mechanochemical route to rctt-1,2,3,4-tetrakis-(4'-carboxyphenyl)-cyclobutane”, Chem. Comm. 46(21) (2010) 3660

  29. M.H. Mir, L.L. Koh, G.K. Tan and J. J. Vittal, "Single-Crystal to Single-Crystal Photochemical Structural Transformations of Interpenetrated 3D Coordination Polymers by [2+2] Cycloaddition Reactions," Angew. Chem. Int. Ed., 49(2) (2010) 390-393

  30. M. H. Mir, L. Wang, M. W. Wong and J. J. Vittal, "Water Helicate, (H2O)7 Hosted by Diamondoid Metal-Organic Framework," Chem. Comm., (30) (2009) 4539

  31. W. L. Leong, A. Y.-Y. Tam, S. K. Batabyal, L. W. Koh, S. Kasapis, V.W.-W. Yam, and J.J. Vittal, "Fluorescence Enhancement of Coordination Polymeric Gel", Chem. Commun., (2008) 3628-3630 (inside cover page)

  32. W.L. Leong, S.K. Batabyal, S. Kasapis and J.J. Vittal, "Fluorescent Magnesium(II) Coordination Polymeric Hydrogel", Chem.- A Eur. J., 14(29) (2008) 8822 (cover page)

  33. M. Nagarathinam and J.J. Vittal, 'Photochemical [2+2] cycloaddition as a tool to study solid state structural transformation,' Chem. Commun., (2008) 438 (back-to-back issues & amongst the top 10 most accessed article from the online version in January 2008)

  34. A.M.P. Peedikakkal and J.J. Vittal, 'Photodimerization of 1D hydrogen-bonded zwitter-ionic lead(II) complex and its isomerization in solution,' Chem. Commun., (2008) 441 (back-to-back issues and cover page)

  35. M.H. Mir & J.J. Vittal, "Phase Transition Accompanied by Transformation of an Elusive Discrete Cyclic Water Heptamer to a Bicyclic (H2O)7 Cluster", Angew. Chem. Int. Ed., 46 (2007) 5925

  36. L. Tian, H.I. Lim, W. Ji, J.J. Vittal, "One pot synthesis and third-order nonlinear optical properties of AgInS2 nanocrystals", Chem. Commun., (2006) 4276. (cover page)

  37. M. Nagarathinam and J.J. Vittal, "Anisotropic movements of coordination polymers upon desolvation: Solid-state transformation of linear 1D coordination polymer to ladder-like structure", Angew. Chem. Int. Ed., 45 (2006) 4337

  38. M.T. Ng, C.B. Boothroyd and J.J. Vittal, "One-pot synthesis of new phase AgInSe2 nanorods", J. Am. Chem. Soc., 128 (2006) 1178

  39. M.T. Ng, C. Boothroyd and J.J. Vittal, "Shape and size control of Ag2Se nanocrystals from single precursor [(Ph3P)3Ag2 (SeC{O}Ph)2]", Chem. Commun., (2005) 3820.(hot article)

  40. N.L. Toh, M. Nagarathinam and J.J. Vittal, "Topochemical photodimerization in the molecular ladder metal coordination polymer [{(CF3CO2)(m-O2CCH3)Zn}2(m-bpe)2]n (where bpe = 4,4'-bipyridylethelene) via single-crystal to single-crystal transformation", Angew. Chem. Int. Ed., 44 (2005) 2237 (cover page)

  41. B. Sreenivasulu and J.J. Vittal, "Helix inside a helix: Encapsulation of Hydrogen-bonded Water Molecules inside a Staircase Coordination Polymer", Angew. Chem. Int. Ed., 43 (2004) 5769. (Highly cited paper by Thomson's Essential Science Indicators, 2004-2010)

  42. M.T. Ng, T.C. Deivaraj, W.T. Klooster, G.J. McIntyre and J.J. Vittal, 'Hydrogen-bonded Polyrotaxane-like structure containing cyclic (H2O)4 in [Zn(OAc)2(m-bpe)]x2H2O: X-Ray and Neutron Diffraction Studies', Chem. Eur. J., 10 (2004) 5853

  43. C.-T. Yang, M. Vetrichelvan, X. Yang, B. Moubaraki, K. S. Murray and J. J. Vittal, 'Syntheses, structural properties and catecholase activity of copper(II) complexes with reduced Schiff base N-(2-hydroxybenzyl)-amino acids', Dalton Trans., (2004) 113 (amongst the top 10 most accessed article through web in Dec. 2003)

  44. M. Lin, K.P. Loh, T.C. Deivaraj and J.J. Vittal, 'Heterogeneous reaction route to CuInS2 thin films', Chem. Commun., (2002) 1400

  45. T.C. Deivaraj, J.H. Park, M. Afzaal, P. O'Brien and J.J. Vittal. 'Single source precursors to ternary silver indium sulfide materials', Chem. Commun., (2001) 2304

  46. C.P. McArdle, J.J. Vittal and R.J. Puddephatt, Molecular topology:Easy self-assembly of an organometallic doubly braided[2]-Catenane, Angew. Chem. Int. Ed.., 39 (2000) 3819

  47. J.D. Ranford, J.J. Vittal, D. Wu and X. Yang,' Thermal Conversion of a Helical Coil to a 3-D Chiral Framework', Angew. Chem. Int. Ed., 38 (1999) 3498

  48. J.D. Ranford, J.J. Vittal and D. Wu, 'Topochemical Conversion of Hydrogen Bonding to Covalent Three Dimensional Networks,' Angew. Chem. Int. Ed., 37 (1998) 1114. (highlighted in Angew. Chem. Int. Ed., 38 (1998) 1211)