Synthesis, Growth, and Characterization of a New Thiourea and Bismuth Chloride Complex with Excellent Nonlinear Optical Properties

Abstract

Crystals of a new organometallic nonlinear optical (NLO) compound, di-μ-chloro-bis[chlorotri(thiourea)bismuth(III)]-pentachloro(thiourea)bismuth-ate(III) (DCBPB), have been successfully grown from formic acid aqueous solutions of thiourea and bismuth chloride by a slow evaporation technique. The crystal structure and atomic composition of DCBPB have been confirmed by single crystal X-ray diffraction (SCXRD), Fourier transform infrared spectra, and elemental analysis. The SCXRD results proved that DCBPB crystallizes in triclinic space group P1 with unit cell dimensions of a = 7.0606(2) Å, b = 8.8106(4) Å, c = 16.3247(8) Å, α = 99.242(4)°, β = 95.309(3)°, γ  = 105.856(3)°, and Z = 2. DCBPB crystal exhibits excellent transmittance from 500 to 2500 nm and green fluorescence with maximum emission at 508 nm. The thermogravimetric-differential scanning calorimetry (TG-DSC) analysis indicates that a solid-phase reaction took place at 170.1 °C, whereas the decomposition temperature of the crystal material was 189 °C. The NLO property obtained by the Kurtz powder test showed that the second harmonic generation efficiency of DCBPB crystal is two-seventh of KDP crystal.

Keywords

NLO / Organometallic / Thiourea / Bismuth chloride / TG–DTA

References

[1] Franken PA, Hill AE, Peters CW, et al. Generation of optical harmonics. Phys Rev Lett, 1961, 7(4): 118-119.

[2] Dmitriev VG, Gurzadyan GG, Nikogosyan DN. Handbook of nonlinear optical crystals, 1999, New York: Springer

[3] Jang SH, Jen AK. Electro-optic (E-O) molecular glasses. Chem Asian J, 2009, 4(1): 20-31.

[4] Wu K, Chen X, Snijders JG, et al. Theoretical studies of nonlinear optical crystals in metal cluster compounds. J Cryst Growth, 2002, 237–239(1): 663-667.

[5] Jiang MH, Fang Q. Organic and semiorganic nonlinear optical materials. Adv Mater, 1999, 11(13): 1147-1151.

[6] Liu XT, Wang XQ, Lin XJ, et al. Growth, characterization and theoretical study of a novel organometallic nonlinear optical crystal: CdHg(SCN)₄(C₂H₅NO)₂. Appl Phys A, 2012, 107(4): 949-957.

[7] Bouchouit K, Essaidi Z, Abed S, et al. Experimental and theoretical studies of NLO properties of organic–inorganic materials base on p-nitroaniline. Chem Phys Lett, 2008, 455(4–6): 270-274.

[8] Lal RB, Frazier DO (2002) Crystal materials for nonlinear optical devices and microgravity science. In: Proceedings of SPIE–the international society for optical engineering, vol 4813

[9] Bouchouit K, Bendeif EE, Ouazzani HE, et al. Correlation between structural studies and third order NLO properties of selected new quinolinium semi-organic compounds. Chem Phys, 2010, 375(1): 1-7.

[10] Kirupavathy SS, Mary SS, Srinivasan P, et al. Investigations on the growth and characterization studies of cadmium thiourea acetate (CTA) single crystals. J Cryst Growth, 2007, 306(1): 102-110.

[11] Bierbach U, Hambley TW, Farrell N. Modification of platinum (II) antitumor complexes with sulfur ligands. 1. Synthesis, structure, and spectroscopic properties of cationic complexes of the types [PtCl(diamine)(L)]NO₃ and [{PtCl(diamine)}₂(L-L)](NO₃)₂(L = monofunctional thiourea derivative; L-L = bifunctional thiourea derivative). Inorg Chem, 1998, 37: 708-716.

[12] Antochshuk V, Olkhovyk O, Jaroniec M, et al. Benzoylthiourea-modified mesoporous silica for mercury(II) removal. Langmuir, 2003, 19(7): 3031-3034.

[13] Di Bella S, Fragalà I, Ledoux I, et al. Synthesis, characterization, optical spectroscopic, electronic structure, and second-order nonlinear optical (NLO) properties of a novel class of donor-acceptor bis(salicylaldiminato)nickel(II) Schiff base NLO chromophores. J Am Chem Soc, 1997, 119(40): 9550-9557.

[14] Xing G, Jiang M, Shao Z, et al. Bis-thiourea cadmium chloride (BTCC)–A novel nonlinear optical crystal of organometallic complex. Chin J Lasers, 1987, 5: 48-54.

[15] Rajasekaran R, Ushasree PM, Jayavel R, et al. Growth and characterization of zinc thiourea chloride (ZTC): a semiorganic nonlinear optical crystal. J Cryst Growth, 2001, 229(1–4): 563-567.

[16] Ushasree PM, Jayavel R, Subramanian C, et al. Growth of zinc thiourea sulfate (ZTS) single crystals: a potential semiorganic NLO material. J Cryst Growth, 1999, 197(1–2): 216-220.

[17] Li M, Li RK. Crystal growth and characterization of a new polymorph of bismuth trithiourea chloride. CrystEngComm, 2013, 15(20): 4176-4180.

[18] Bhat SG, Dharmaprakash SM. A new metal-organic crystal: bismuth thiourea chloride. Mater Res Bull, 1998, 33(6): 833-840.

[19] Krishnakumar V, Saleem SS, Prasad LG. Crystal structure, vibrational, and optical investigations of semiorganic nonlinear optical crystal: Bi3[CS(NH2)2]9Cl9 2H2O. J Raman Spectrosc, 2009, 40(8): 1011-1015.

[20] Kurtz SK, Perry TT. A powder technique for the evaluation of nonlinear optical materials. J Appl Phys, 1968, 39: 3798-3813.

[21] Yamaguchi A, Penland RB, Mizushima S, et al. Infrared absorption spectra of inorganic coördination complexes. XIV. Infrared studies of some metal thiourea complexes^1a. J Am Chem Soc, 1958, 80(3): 527-529.

[22] Alı́A JM, Edwards HGM, Stoev MD (1999) A systematic FT-Raman spectroscopic study of twelve bis-thiourea complexes, A(tu)2B2(A = Zn, Cd, Hg; B = Cl, Br, I, SCN). Spectrochim Acta Part A Mol Biomol Spectrosc 55(12):2423–2435

[23] Brunetti B, Gozzi D, Iervolino M, et al. Bismuth activity in lead-free solder Bi–In–Sn alloys. CALPHAD Comput Coupling Phase Diagrams Thermochem, 2006, 30(4): 431-442.

[24] Anis M, Shaikh RN, Shirsat MD, et al. Investigation of optical and electrical properties of L-Cystein doped zinc thiourea chloride (ZTC) crystal for nonlinear optical (NLO) applications. Opt Laser Technol, 2014, 60: 124-129.

[25] Madarász J, Bombicz P, Okuya M, et al. Online coupled TG–FTIR and TG/DTA–MS analyses of the evolved gases from dichloro(thiourea) tin(II). Solid State Ionics, 2004, 172(1–4): 577-581.

[26] Madarász J, Krunks M, Niinistö L, et al. Evolved gas analysis of dichlorobis(thiourea) zinc(II) by coupled TG-FTIR and TG/DTA-MS techniques. J Therm Anal Calorim, 2004, 78(2): 679-686.