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Experimental and Theoretical Investigations of Tetrakis (Thiourea) Palladium Chloride Semi-Organic Non-Linear Optical Crystal: An Approach to NLO Application

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Abstract

Semi-organic non-linear optical crystals of tetrakis (thiourea) palladium chloride (TTPC) were synthesized by a slow evaporation method. X-ray diffraction analysis performed on the title crystal established its orthorhombic structure and Pna2 1 space group. The crystalline perfection was investigated by means of high resolution X-ray diffraction (HRXRD) measurements. The values of transmittance, cutoff wavelength, refractive index and single oscillator parameters were computed through ultraviolet (UV) transmittance analysis. The second harmonic generation efficiency (SHG) of the TTPC crystals was verified by the Kurtz Perry technique. The potential of TTPC to act as a NLO material was further envisaged by the hyperpolarizability studies which resulted in higher values of dipoles and polarizability. To shed light on the pattern of charge distribution and donor-acceptor interactions prevailing in TTPC crystals, natural bond orbital (NBO) analysis was performed. Laser damage threshold (LDT) analysis on TTPC resulted in a LDT value of 5.1 GW/cm 2. The low birefringence value calculated from birefringence patterns attested the to suitability of the crystal to be used in harmonic generation devices. Using the HOMO-LUMO approach the values of significant global chemical molecular reactivity descriptors were determined.

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References

  1. Singer K, Sohn JE (1986) Second harmonic generation in poled polymer films. Appl Phys Lett 49:248–250

    Article  CAS  Google Scholar 

  2. Senthil Murugan G, Ramasamy P (2009) Growth and characterization of metal-organic crystal: tetra thiourea cobalt chloride (TTCoC). J Cryst Growth 311:585–588

    Article  Google Scholar 

  3. Lopes JGS, de Oliveira LFC, Edwards HGM, Santos PS (2004) The Raman spectrum of thiourea–oxocarbon adducts. J Raman Spectrosc 35:131–139

  4. Ushashree PM, Jayavel R, Subramanian C, Ramasamy P (1999) Growth of zinc thiourea sulfate (ZTS) single crystals: a potential semiorganic NLO material. J Cryst Growth 197:216–220

    Article  Google Scholar 

  5. Sangwal K (1989) Micro morphology of as grown surfaces of crystals. Prog Cryst Growth Charact 19:189–245

    Article  CAS  Google Scholar 

  6. Rajagopalan NR, Krishnamoorthy P (2017) A systematic approach to physico-chemical analysis of tris (thiourea) zinc selenate – a semi-organic nonlinear optical crystal. Optik: International Journal for Light and Electron Optics 129:118–129

    Article  CAS  Google Scholar 

  7. Rajagopalan NR, Krishnamoorthy P (2016) Contemporary studies on growth and characterization of bis (thiourea) strontium chloride—A potential optoelectronic NLO material. Optik: International Journal for Light and Electron Optics 27:3582–3589

    Article  Google Scholar 

  8. Rajagopalan NR, Krishnamoorthy P, Jayamoorthy K (2017) A strategic approach to physico-chemical analysis of bis (thiourea) lead chloride – a reliable semi-organic nonlinear optical crystal. Opt laser technol 89:6–15

    Article  CAS  Google Scholar 

  9. Anand S, Sundarajan RS, Ramachandraraja C, Ramalingam S, Durga R (2015) Molecular vibrational investigation [FT-IR, FT-Raman, UV–Visible and NMR] on Bis(thiourea) Nickel chloride using HF and DFT calculations. Spectrochim Acta A 138:203–215

    Article  CAS  Google Scholar 

  10. Rajagopalan NR, Krishnamoorthy P, Jayamoorthy K, Austeria M (2016) Bis (thiourea) strontium chloride as promising NLO material : an experimental and theoretical study. Karbala International Journal of Modern Science. doi:10.1016/j.kijoms.2016.08.001

  11. Muthu K, Meenatchi V, Rajasekar M, Aditya Prasad A, Meena K, Agilandeshwari R, Kanagarajan V, Meenakshisundaram SP (2015) Combined theoretical and experimental studies on the molecular structure, spectral and Hirshfeld surface studies of NLO tris(thiourea)zinc(II) sulfate crystals. J Mol Struct 1091:210–221

    Article  CAS  Google Scholar 

  12. Berta DA, Spofford WA, Boldrini P, Amma EL (1970) Crystal and molecular structure of tetrakis (thiourea) palladium (II) chloride. Inorg Chem 9:136–142

    Article  CAS  Google Scholar 

  13. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr JA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford, CT

  14. Padmaja L, Ravikumar C, Sajan D, Joe IH, Jayakumar VS, Pettit GR, Neilsen OF (2009) Density functional study on the structural conformations and intramolecular charge transfer from the vibrational spectra of the anticancer drug combretastatin-A2. J Raman Spectrosc 40:419–428

    Article  CAS  Google Scholar 

  15. Ravikumar C, Joe IH, Jayakumar VS (2008) Charge transfer interactions and nonlinear optical properties of push–pull chromophore benzaldehyde phenylhydrazone: a vibrational approach. Chem Phys Lett 460:552–558

    Article  CAS  Google Scholar 

  16. Bhagavannarayana G, Parthiban S, Meenakshisundaram S (2006) Enhancement of crystalline perfection by organic dopants in ZTS, ADP and KHP crystals as investigated by high-resolution XRD and SEM. J Appl Crystallogr 39:784–790

    Article  CAS  Google Scholar 

  17. Batterman BW, Cole H (1964) Dynamical diffraction of x rays by perfect crystals. Rev Mod Phys 36:681–717

    Article  CAS  Google Scholar 

  18. Balarew C, Duhlev R (1984) Application of the hard and soft acids and bases concept to explain ligand coordination in double salt structures. J Solid State Chem 55:1–6

    Article  Google Scholar 

  19. Martin Britto S, Natarajan S (2008) Growth and characterization of two new NLO materials from the amino acid family: l-Histidine nitrate and l-Cysteine tartrate monohydrate. Opt Commun 281:457–462

    Article  Google Scholar 

  20. Dhanaraj PV, Suthan T, Rajesh NP (2010) Synthesis, crystal growth and characterization of a semiorganic material: calcium dibromide bis(glycine) tetrahydrate. Curr Appl Phys 10:1349–1353

    Article  Google Scholar 

  21. Wemple SH, DiDomenico M (1971) Behavior of the electronic dielectric constant in covalent and ionic materials. Phys Rev B 3:1338–1351

    Article  Google Scholar 

  22. Sabari Girisun TC, Dhanuskodi S (2009) Linear and nonlinear optical properties of tris thiourea zinc sulphate single crystals. Cryst Res Technol 44:1297–1302

    Article  Google Scholar 

  23. Kurtz SK, Perry TT (1968) A powder technique for the evaluation of nonlinear optical materials. J Appl Phys 39:3798–3812

    Article  CAS  Google Scholar 

  24. Steiger D, Ahlbrandt C, Glaser R (1998) Crystal potential formula for the calculation of crystal lattice sums. J Phys Chem B 102:4257–4260

    Article  CAS  Google Scholar 

  25. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, et al. (2004) Gaussian 03 Revision C.02, Gaussian, Inc. Wallingford, CT

  26. Mulliken RS (1955) Electronic population analysis on LCAO-MO molecular wave functions. J Chem Phys 23:1833–1840

    Article  CAS  Google Scholar 

  27. Jayabharathi J, Thanikachalam V, Jayamoorthy K, Venkatesh Perumal M (2011) A physiochemical study of excited state intramolecular proton transfer process: luminescent chemosensor by spectroscopic investigation supported by ab initio calculations. Spectrochim Acta A 79:6–16

    Article  CAS  Google Scholar 

  28. Jayabharathi J, Thanikachalam V, Jayamoorthy K (2013) Optical properties of 1,2-diaryl benzimidazole derivatives – a combined experimental and theoretical studies. Spectrochim Acta A 115:74–78

    Article  CAS  Google Scholar 

  29. Jayabharathi J, Thanikachalam V, Srinivasan N, Jayamoorthy K (2011) Synthesis and physicochemical studies of bioactive heterocycles as sensitive NLO materials. Spectrochim Acta A 83:329–336

    Article  CAS  Google Scholar 

  30. Jayabharathi J, Thanikachalam V, Srinivasan N, Venkatesh Perumal M, Jayamoorthy K (2011) Physiochemical studies of molecular hyperpolarisability of imidazole derivatives. Spectrochim Acta A 79:137–147

    Article  CAS  Google Scholar 

  31. Jayabharathi J, Thanikachalam V, Jayamoorthy K (2012) Photophysical studies of some heterocyclic chromophores as potential NLO materials. Spectrochim Acta A 89:301–307

    Article  CAS  Google Scholar 

  32. Jayabharathi J, Thanikachalam V, Jayamoorthy K (2012) Computational studies of 1,2-disubstituted benzimidazole derivatives. Spectrochim Acta A 97:131–136

    Article  CAS  Google Scholar 

  33. Szafran M, Komasa A, Adamska EB (2007) Crystal and molecular structure of 4-carboxypiperidinium chloride (4-piperidinecarboxylic acid hydrochloride). J Mol Struct 827:101–107

    Article  CAS  Google Scholar 

  34. Nakatani H, Bosenberg WR, Cheng LK, Tang CL (1988) Laser induced damage in beta barium meta borate. Appl Phys Lett 53:2587–2589

    Article  CAS  Google Scholar 

  35. Buse K, Luennemann M, Imaging 3D (2000) Wave front sensing utilizing a birefringent crystal. Phys Rev Lett 85:3385– 3387

    Article  CAS  Google Scholar 

  36. Vijayan N, Nagarajan K, Slawin AMZ, Shasidharan Nair CK, Bhagavannarayana G (2007) Growth of benzimidazole single crystal by Sankaranarayanan–Ramasamy method and its characterization by high-resolution x-ray diffraction, thermogravimetric/differential thermal analysis, and birefringence studies. Crys Growth Des 7:445–448

    Article  CAS  Google Scholar 

  37. Krishnan P, Gayathri K, Rajkumar PR, Jayaramakrishnan V, Gunasekaran S, Anbalagan G (2014) Studies on crystal growth, vibrational, optical, thermal and dielectric properties of new organic nonlinear optical crystal: Bis (2,3-dimethoxy-10-oxostrychnidinium) phthalate nonahydrate single crystal. Spectrochim Acta A 131:114–124

    Article  CAS  Google Scholar 

  38. Parr RG, Szentpaly LV, Liu S (1999) Electrophilicity index. J Am Chem Soc 121:1922–1924

    Article  CAS  Google Scholar 

  39. Parr RG, Chattaraj PK (1991) Principle of maximum hardness. J Am Chem Soc 113:1854–1855

    Article  CAS  Google Scholar 

  40. Parthasarathy R, Subramanian V, Roy DR, Chattaraj PK (2004) Electrophilicity index as a possible descriptor of biological activity. Bioorg Med Chem 12:5533–5543

    Article  Google Scholar 

  41. Pauling L (1960) The nature of the chemical bond, 3rd edn. Cornell University Press, Ithaca, New York

    Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, St. Joseph’s College of Engineering, Chennai, 600119, Tamilnadu, India

    N. R. Rajagopalan & K. Jayamoorthy

  2. Department of Chemistry, Bharathiar University R & D Centre, Coimbatore, 641046, Tamilnadu, India

    N. R. Rajagopalan

  3. Department of Chemistry, Dr. Ambedkar Government Arts College, Chennai, 600039, Tamilnadu, India

    P. Krishnamoorthy

Authors
  1. N. R. Rajagopalan
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  2. P. Krishnamoorthy
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  3. K. Jayamoorthy
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Correspondence to P. Krishnamoorthy.

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Rajagopalan, N.R., Krishnamoorthy, P. & Jayamoorthy, K. Experimental and Theoretical Investigations of Tetrakis (Thiourea) Palladium Chloride Semi-Organic Non-Linear Optical Crystal: An Approach to NLO Application. Silicon 10, 841–850 (2018). https://doi.org/10.1007/s12633-016-9538-1

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  • DOI: https://doi.org/10.1007/s12633-016-9538-1

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