- Email: [email protected]
Supramolecular architecture, characterization and computational studies of hydrazinium picrate – An organic charge transfer crystal
vailable online at www.sciencedirect.com
ScienceDirect Materials Today: Proceedings 15 (2019) 654–662
www.materialstoday.com/proceedings
ICMAM-2018
Supramolecular architecture, characterization and computational studies of hydrazinium picrate – An organic charge transfer crystal S. Sivaramana, R. Markkandana,b* and SP. Meenakshisundarama a
Department of Chemistry, Annamalai University, Annamalainagar-608 002, Tamilnadu, India Department of Chemistry, Thiru Govindasamy Government Arts College, Tindivanam, India
b
Abstract
Single crystals of 2-furichydrazinium picrate monohydrate (FHM) grown from ethanol at room temperature belong to the space group P21/c as elucidated from X-ray analysis. Supramolecular assembly is constructed by weak C-H…O, N-H…O and π-π stacking interactions. Intermolecular interactions are analysed by Hirshfeld surface. It exhibits optical limiting property and third-order nonlinear optical character as revealed by Z-scan studies. Band gap energy was estimated by Kubelka-Munk
algorithm. Molecular interactions were quantified by Hirshfeld surface analysis and supported well the experimental results. © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
Keywords: Supramolecular architecture; Charge transfer; Hirshfeld analysis; Nonlinear optical material
*Email address: [email protected]
2214-7853 © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
655
1. Introduction Picric acid undergoes complexation with a number of electron donor compounds through H-bond interactions. Recently, numbers of hydrazide complexes possessing high nonlinearity are reported [1-3]. As a part of our investigations [4-10] in the studies of proton transfer compounds and their NLO characterization this work was undertaken. Molecular structures of 4-nitrophenylhydrazinium picrate monohydrate [11] and 1methylhydrazinium picrate [12] have been reported. Here, we demonstrate the synthesis, supramolecular architecture, Hirshfeld surface analysis, first order molecular hyperpolarizability and optical nonlinearity of title compound. 2.0 Experimental 2.1 Synthesis FHM was obtained by mixing equimolar quantities of picric acid and 2-furic hydrazide in C2H5OH medium. Single crystals were grown and subjected to characterization studies. Crystal image, morphology and SEM of FHM are shown in Fig.1. a
b
c
Fig.1 (a) Photo image (b) Crystal morphology (c) SEM image
2. Results and discussion 2.1 FT-IR spectroscopy Vibrational FT-IR spectrum of FHM is shown in Fig.2.The band at 1614 cm−1 is due to ʋ(N-H) stretching frequency. The phenolic O vibration is observed at 1158 cm−1. The ʋ (NH(NH3+) symmetric stretching vibration appeared at ~3098 cm−1. The ʋ (O-H) stretching vibrations appear at ~3593 cm−1 and ʋ (NO2) appeared as sharp intensity band at ~1333 cm−1.
Fig.2 Vibrational spectrum of FHM
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S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
2.2 XRD analysis Experimental XRD profiles show phase purity and good crystallinity (Fig.3). The XRD is simulated using single crystal X-ray diffraction data and it is in good agreement with experimental pattern. Intensity variations are justified in our previous publications [5, 8].
Fig. 3 Powder XRD patterns
Single crystal X-ray crystallographic studies reveal that FHM crystallizes centrosymmetrically (P21/c). The lattice parameters are, a = 16.014(18), b = 6.954(8), c = 14.716 and z = 4(R1 = 0.1153, wR2 = 0.1292). An ORTEP view and packing diagram of FHM are shown in Fig.4. The structure comprises one 2-furic hydrazinium cation and one picrate anion coordinated to one water molecule. The donor and acceptor molecules of complex are held together by van der Waals interactions. The bond lengths of C(1)–C(2) and C(1)–C(6)˚ are 1.449(4) and 1.450(4) Å respectively(longer than C-C distances). The following observations clearly reveal proton transfer as reported in other picrates [5-10]. (i) Bond distance of C(1)-O(7) is in between single and double bonds. (ii) Specific electron delocalization around C(1) because of O(7) hydroxyl proton transfer. Crystal cohesion is achieved by hydrogen bonds, short contacts and van der Walls interactions. Table 1 lists the hydrogen bonds and symmetry transformations. The strong hydrogen bonds like O–H....O and N–H....O contribute to charge transfer, hence nonlinearity and resulting in nonlinear optical character. Weak intermolecular interactions N(5)-H(5A)....O(6), N(5)-H(5A)....O(9) and C(9)-H(9)....O(1) are observed with respective bond distances 2.66(3), 2.64(3) and 2.63Å. a
b
Fig.4 a) ORTEP of FHM b) Crystal packing in the unit cell
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The π - π, C-H.…O and N-H…O hydrogen bonds established the geometry of 2-furic hydrazinium picrate monohydrate. Fig.5a illustrates the weak π – π interactions. The N-H…O and C-H…O interactions are given in Figs.5b and 5c. The average π – π interaction distance is ~ 3.435 Å. Crystal structure of FHM exhibits both interand intramolecular hydrogen bonding interactions with different supramolecular infrastructures.
a)
π -π
b)
c)
N-H...O
C-H...O
Fig.5 Crystal packing a) π-π b) N-H...O and C-H...O interactions
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S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
Table 1 Hydrogen bonds (selective) for FHM [Å and °]. D-H...A C(10)-H(10)...O(4)#2 C(11)-H(11)...O(3)#3 O(10)-H(10A)...O(6) O(10)-H(10A)...O(7) N(4)-H(4A)...O(10) N(5)-H(5C)...O(5)#6 N(5)-H(5C)...O(10)#7
d(D-H) 0.93 0.93 0.847(18) 0.847(18) 0.838(18) 0.863(16) 0.863(16)
d(H...A) 2.56 2.37 2.05(3) 2.09(3) 1.96(2) 2.58(3) 2.071(18)
d(D...A) 3.174(4) 3.165(4) 2.768(3) 2.767(3) 2.770(4) 3.079(4) 2.890(5)
<(DHA) 123.7 143.9 142(3) 137(3) 163(3) 118(3) 158(3)
2.3 UV-Vis-NIR diffuse reflectance spectrum Minimum absorption with a cut –off λ of ~509 nm is observed experimentally. The direct band gap energy of the specimen is estimated by Kubelka-Munk algorithm and it is estimated as 2.44 eV as shown in Fig. 6.
Fig.6 Band gap energy (Direct)
2.4 First-order molecular hyperpolarizability (β) β was estimated using urea as reference material and it is equal to 9.7703 × 10−30 e.s.u (37 times of reference material). Nonzero (β) values result in large beta value, which is associated with charge transfer. Intra-and intermolecular hydrogen bonding interactions are the prime reason for large micro level nonlinearity. As seen from Table 2 β component has a high value along x-axis. Table 2. First-order molecular hyperpolarizability (β) of FHM First-order molecular hyperpolarizability βxxx 1370.642 βxxy -418.773 -434.890 βxyy βyyy -31.537 -57.925 βxxz βxyz -149.809 152.135 βyyz βxzz 79.453 -26.547 βyzz βzzz 50.596 βtot ( X 10-30)esu
9.770
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2.5 Frontier molecular orbitals Prominent donor orbitals (HOMO) and prominent acceptor orbitals (LUMO) are shown in Fig.7. HOMOLUMO energy was calculated by GAUSSIAN 09W [13, 14]. Density functional theory calculation reveals that ∆E = 3.89 eV. Theoretical value is higher than the experimental one because of change of phase [15].
Fig.7 Surfaces of Frontier Molecular Orbitals
2.6 Hirshfeld surfaces analysis The Hirshfeld surfaces [16-18] visualized using Crystal Explorer (Version 3.1) are shown in Fig.8. The electron density surface curves are indicated by curvedness surface (Fig 8d). Shapeindex provides π-π interaction information(Fig 8e). Major interactions are, O….H and H….O (53.4%). Minor interactions are N….H & H….N (2.4%) C….H & H….C (6.9%), H….H (9.9%) and C-C (7.6%)(π-π). Quantification of molecular interactions are given as finger print plots (Fig.9).
a
b
c
d
Fig.8 Hirshfeld surfaces (a) dnorm (b) di (c) de (d) curvedness (e) shape index
e
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S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
Fig.9 2D Fingerprint plots
2.7 Z-scan studies Z-scan experiment was carried out to have idea about third-order effect. The obtained open aperture curve (inset of Fig. 10) shows the reverse saturation behavior (RSA) and hence the absorption coefficient β is positive.
2 2T …… (1) I0 Leff where ΔT is indicating minimum transmittance value at the open aperture Z-scan curve. Plot of normalized stransmittance versus input influence is shown as Fig.10. There is no change in transmittance at low input fluencies and it decreases markedly as irradiance fluence exceeded 23.65 J cm-2. The deviation of linear transmittance is a typical characteristic of optical limiting phenomena [19]. Two photon absorption mechanism [20] could be the possible reason for the observed behaviour. The 2-furichydrazinium picrate shows good optical limiting behavior (Table 3) and hence useful for optical limiting applications [21, 22].
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Fig.10 Fluence-dependent transmittance behaviour of FHM Table 3. Z- scan experimental data β ×10-12 (m/W)
4.0924
χ(3) × 10-13 (e.s.u)
1.3427
Optical limiting (J cm-2)
23.65
3. Conclusions The paper describes the supramolecular architecture of 2-furichydrazinium picrate monohydrate (FHM) by X-ray diffraction analysis. Band gap energy was estimated by Kubelka-Munk algorithm. Molecular interactions are quantified by Hirshfeld surface analysis well supporting the experimental results. H-bonding interactions (53.4%) are dominant and hence create a favorable atmosphere for nonlinearity. The title charge transfer complex exhibits third order nonlinear character as revealed by Z-scan studies. Observed nonlinearity can be ascribed to intra-and intermolecular hydrogen interactions bonding, which is also responsible for crystal cohesion. Acknowledgements The authors express thanks the Council of Scientific and Industrial Research (CSIR), New Delhi, for financial support through research grant No. 21 (1024)/16/EMR-II, and S.S is thankful to CSIR project for the award of SRF. References 1. D. Nagal, A. K. Saxena, J. Ceram.Soc., 38 (2015) 45-56. 2. A. Manimekalai, N. Saradhadevi, A. Thiruvalluvar, Spectrochim Acta., Part A, 77 (2010) 687–695. 3. V. Meenatchi, K. Muthu, M. Rajasekar, G. Bhagavannarayana, SP. Meenakshisundaram, Optik, 125 (2014) 4181–4185. 4. A. Aditya Prasad,K. Muthu, V. Meenatchi, M. Rajasekar, S. P. Meenakshisundaram, S. C. Mojumdar, J Therm Anal Calorim. 119 (2015) 885–890 5. A. Aditya Prasad, K. Muthu, M. Rajasekar , V. Meenatchi , SP. Meenakshisundaram , Spectrochim.Acta A , 135 (2015) 46-54. 6. A.Aditya Prasad, K.Muthu, M.Rajasekar, V.Meenatchi, S.P.Meenakshisundaram, Spectrochim. Acta A, 135 (2015) 805-813 7. G. Ramasamy, Subbiah Meenakshisundaram, Optik, 2014(125) 4422-4426 8. S. Sivaraman, C. Balakrishnana, A. Aditya Prasadb, R. M. Sokalingama, S. P. Meenakshisundarama, R. Markkandan, Mol. Cryst. Liq. Cryst. 165(2017)153-168.
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9. A. Aditya Prasad, S.Kalainathan, S. P. Meenakshisundaram, Optick, 127(2016) 6134-6149 10. A . Agilandeswari, A. Aditya Prasad, S. Sivaraman, S.Kalainathan, S. P. Meenakshisundaram, Mol. Cryst. Liq. Cryst. 265(2015) 238252 11. Hong-lan Cai, Bing Liu and Qing-an Qiao, Acta Cryst., E70(2014) o15. 12. Xiao-Gang Mu., Xuan- Jun Wang., Youzhi Zhang., Xiaoli Gou., & Xia Li. (2011). Acta Cryst, E67, o3378. 13. 2009M. J. Frisch, G.W. Trucks,. Gaussian 09, Revision C.01, Gaussian, Inc., Wallingford, CT. 2009 14. R.Dennington, T. Keith, J. Millam,. Gauss View, Version 5, Semichem Inc., Shawnee Mission KS. 15. RO. MU. Jauhar, P. Murugakoothan,. AIP Conf. Proc, 1832 (2017)100005. 16. M. A.Spackman, D. Jayatilaka. CrystEngComm, 11(2009)19–32. 17. F. L. Hirshfeld, Theor. Chim. Acta, 44 (1977)129–138. 18. S. K. Wolff, D. J. Grimwood, J. J. McKinnon, M. J. Turner, D. Jayatilaka, M. A. SpackmanCrystalExplorer (Version3.1), University of Western Australia., 2012. 19. Hendry I. Elim, Jian Yang, Jim-Yang Lee, Jun Mi, Wei Ji, Appl. Phys. Lett. 88(2006) 083107 20. He, G. S.; Tan, L. S.; Zheng, Q.; Prasad, P. N. Chem. Rev., 108(2008)1245. 21. Lakshminarayana Polavarapu, Qing-Hua Xu, Mohan S. Dhoni, Wei Ji, Appl. Phys. Lett. 92 (2008) 263110 22. Geok-Kieng Lim, Zhi-Li Chen, Jenny Clark, Roland G. S. Goh, Wee-Hao Ng, Hong-Wee Tan, Richard H. Friend, Peter K. H. Ho, LayLay Chua, Nat.Photonics,5 (2011) 554.
ScienceDirect Materials Today: Proceedings 15 (2019) 654–662
www.materialstoday.com/proceedings
ICMAM-2018
Supramolecular architecture, characterization and computational studies of hydrazinium picrate – An organic charge transfer crystal S. Sivaramana, R. Markkandana,b* and SP. Meenakshisundarama a
Department of Chemistry, Annamalai University, Annamalainagar-608 002, Tamilnadu, India Department of Chemistry, Thiru Govindasamy Government Arts College, Tindivanam, India
b
Abstract
Single crystals of 2-furichydrazinium picrate monohydrate (FHM) grown from ethanol at room temperature belong to the space group P21/c as elucidated from X-ray analysis. Supramolecular assembly is constructed by weak C-H…O, N-H…O and π-π stacking interactions. Intermolecular interactions are analysed by Hirshfeld surface. It exhibits optical limiting property and third-order nonlinear optical character as revealed by Z-scan studies. Band gap energy was estimated by Kubelka-Munk
algorithm. Molecular interactions were quantified by Hirshfeld surface analysis and supported well the experimental results. © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
Keywords: Supramolecular architecture; Charge transfer; Hirshfeld analysis; Nonlinear optical material
*Email address: [email protected]
2214-7853 © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
655
1. Introduction Picric acid undergoes complexation with a number of electron donor compounds through H-bond interactions. Recently, numbers of hydrazide complexes possessing high nonlinearity are reported [1-3]. As a part of our investigations [4-10] in the studies of proton transfer compounds and their NLO characterization this work was undertaken. Molecular structures of 4-nitrophenylhydrazinium picrate monohydrate [11] and 1methylhydrazinium picrate [12] have been reported. Here, we demonstrate the synthesis, supramolecular architecture, Hirshfeld surface analysis, first order molecular hyperpolarizability and optical nonlinearity of title compound. 2.0 Experimental 2.1 Synthesis FHM was obtained by mixing equimolar quantities of picric acid and 2-furic hydrazide in C2H5OH medium. Single crystals were grown and subjected to characterization studies. Crystal image, morphology and SEM of FHM are shown in Fig.1. a
b
c
Fig.1 (a) Photo image (b) Crystal morphology (c) SEM image
2. Results and discussion 2.1 FT-IR spectroscopy Vibrational FT-IR spectrum of FHM is shown in Fig.2.The band at 1614 cm−1 is due to ʋ(N-H) stretching frequency. The phenolic O vibration is observed at 1158 cm−1. The ʋ (NH(NH3+) symmetric stretching vibration appeared at ~3098 cm−1. The ʋ (O-H) stretching vibrations appear at ~3593 cm−1 and ʋ (NO2) appeared as sharp intensity band at ~1333 cm−1.
Fig.2 Vibrational spectrum of FHM
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2.2 XRD analysis Experimental XRD profiles show phase purity and good crystallinity (Fig.3). The XRD is simulated using single crystal X-ray diffraction data and it is in good agreement with experimental pattern. Intensity variations are justified in our previous publications [5, 8].
Fig. 3 Powder XRD patterns
Single crystal X-ray crystallographic studies reveal that FHM crystallizes centrosymmetrically (P21/c). The lattice parameters are, a = 16.014(18), b = 6.954(8), c = 14.716 and z = 4(R1 = 0.1153, wR2 = 0.1292). An ORTEP view and packing diagram of FHM are shown in Fig.4. The structure comprises one 2-furic hydrazinium cation and one picrate anion coordinated to one water molecule. The donor and acceptor molecules of complex are held together by van der Waals interactions. The bond lengths of C(1)–C(2) and C(1)–C(6)˚ are 1.449(4) and 1.450(4) Å respectively(longer than C-C distances). The following observations clearly reveal proton transfer as reported in other picrates [5-10]. (i) Bond distance of C(1)-O(7) is in between single and double bonds. (ii) Specific electron delocalization around C(1) because of O(7) hydroxyl proton transfer. Crystal cohesion is achieved by hydrogen bonds, short contacts and van der Walls interactions. Table 1 lists the hydrogen bonds and symmetry transformations. The strong hydrogen bonds like O–H....O and N–H....O contribute to charge transfer, hence nonlinearity and resulting in nonlinear optical character. Weak intermolecular interactions N(5)-H(5A)....O(6), N(5)-H(5A)....O(9) and C(9)-H(9)....O(1) are observed with respective bond distances 2.66(3), 2.64(3) and 2.63Å. a
b
Fig.4 a) ORTEP of FHM b) Crystal packing in the unit cell
S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
657
The π - π, C-H.…O and N-H…O hydrogen bonds established the geometry of 2-furic hydrazinium picrate monohydrate. Fig.5a illustrates the weak π – π interactions. The N-H…O and C-H…O interactions are given in Figs.5b and 5c. The average π – π interaction distance is ~ 3.435 Å. Crystal structure of FHM exhibits both interand intramolecular hydrogen bonding interactions with different supramolecular infrastructures.
a)
π -π
b)
c)
N-H...O
C-H...O
Fig.5 Crystal packing a) π-π b) N-H...O and C-H...O interactions
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Table 1 Hydrogen bonds (selective) for FHM [Å and °]. D-H...A C(10)-H(10)...O(4)#2 C(11)-H(11)...O(3)#3 O(10)-H(10A)...O(6) O(10)-H(10A)...O(7) N(4)-H(4A)...O(10) N(5)-H(5C)...O(5)#6 N(5)-H(5C)...O(10)#7
d(D-H) 0.93 0.93 0.847(18) 0.847(18) 0.838(18) 0.863(16) 0.863(16)
d(H...A) 2.56 2.37 2.05(3) 2.09(3) 1.96(2) 2.58(3) 2.071(18)
d(D...A) 3.174(4) 3.165(4) 2.768(3) 2.767(3) 2.770(4) 3.079(4) 2.890(5)
<(DHA) 123.7 143.9 142(3) 137(3) 163(3) 118(3) 158(3)
2.3 UV-Vis-NIR diffuse reflectance spectrum Minimum absorption with a cut –off λ of ~509 nm is observed experimentally. The direct band gap energy of the specimen is estimated by Kubelka-Munk algorithm and it is estimated as 2.44 eV as shown in Fig. 6.
Fig.6 Band gap energy (Direct)
2.4 First-order molecular hyperpolarizability (β) β was estimated using urea as reference material and it is equal to 9.7703 × 10−30 e.s.u (37 times of reference material). Nonzero (β) values result in large beta value, which is associated with charge transfer. Intra-and intermolecular hydrogen bonding interactions are the prime reason for large micro level nonlinearity. As seen from Table 2 β component has a high value along x-axis. Table 2. First-order molecular hyperpolarizability (β) of FHM First-order molecular hyperpolarizability βxxx 1370.642 βxxy -418.773 -434.890 βxyy βyyy -31.537 -57.925 βxxz βxyz -149.809 152.135 βyyz βxzz 79.453 -26.547 βyzz βzzz 50.596 βtot ( X 10-30)esu
9.770
S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
659
2.5 Frontier molecular orbitals Prominent donor orbitals (HOMO) and prominent acceptor orbitals (LUMO) are shown in Fig.7. HOMOLUMO energy was calculated by GAUSSIAN 09W [13, 14]. Density functional theory calculation reveals that ∆E = 3.89 eV. Theoretical value is higher than the experimental one because of change of phase [15].
Fig.7 Surfaces of Frontier Molecular Orbitals
2.6 Hirshfeld surfaces analysis The Hirshfeld surfaces [16-18] visualized using Crystal Explorer (Version 3.1) are shown in Fig.8. The electron density surface curves are indicated by curvedness surface (Fig 8d). Shapeindex provides π-π interaction information(Fig 8e). Major interactions are, O….H and H….O (53.4%). Minor interactions are N….H & H….N (2.4%) C….H & H….C (6.9%), H….H (9.9%) and C-C (7.6%)(π-π). Quantification of molecular interactions are given as finger print plots (Fig.9).
a
b
c
d
Fig.8 Hirshfeld surfaces (a) dnorm (b) di (c) de (d) curvedness (e) shape index
e
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S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
Fig.9 2D Fingerprint plots
2.7 Z-scan studies Z-scan experiment was carried out to have idea about third-order effect. The obtained open aperture curve (inset of Fig. 10) shows the reverse saturation behavior (RSA) and hence the absorption coefficient β is positive.
2 2T …… (1) I0 Leff where ΔT is indicating minimum transmittance value at the open aperture Z-scan curve. Plot of normalized stransmittance versus input influence is shown as Fig.10. There is no change in transmittance at low input fluencies and it decreases markedly as irradiance fluence exceeded 23.65 J cm-2. The deviation of linear transmittance is a typical characteristic of optical limiting phenomena [19]. Two photon absorption mechanism [20] could be the possible reason for the observed behaviour. The 2-furichydrazinium picrate shows good optical limiting behavior (Table 3) and hence useful for optical limiting applications [21, 22].
S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
661
Fig.10 Fluence-dependent transmittance behaviour of FHM Table 3. Z- scan experimental data β ×10-12 (m/W)
4.0924
χ(3) × 10-13 (e.s.u)
1.3427
Optical limiting (J cm-2)
23.65
3. Conclusions The paper describes the supramolecular architecture of 2-furichydrazinium picrate monohydrate (FHM) by X-ray diffraction analysis. Band gap energy was estimated by Kubelka-Munk algorithm. Molecular interactions are quantified by Hirshfeld surface analysis well supporting the experimental results. H-bonding interactions (53.4%) are dominant and hence create a favorable atmosphere for nonlinearity. The title charge transfer complex exhibits third order nonlinear character as revealed by Z-scan studies. Observed nonlinearity can be ascribed to intra-and intermolecular hydrogen interactions bonding, which is also responsible for crystal cohesion. Acknowledgements The authors express thanks the Council of Scientific and Industrial Research (CSIR), New Delhi, for financial support through research grant No. 21 (1024)/16/EMR-II, and S.S is thankful to CSIR project for the award of SRF. References 1. D. Nagal, A. K. Saxena, J. Ceram.Soc., 38 (2015) 45-56. 2. A. Manimekalai, N. Saradhadevi, A. Thiruvalluvar, Spectrochim Acta., Part A, 77 (2010) 687–695. 3. V. Meenatchi, K. Muthu, M. Rajasekar, G. Bhagavannarayana, SP. Meenakshisundaram, Optik, 125 (2014) 4181–4185. 4. A. Aditya Prasad,K. Muthu, V. Meenatchi, M. Rajasekar, S. P. Meenakshisundaram, S. C. Mojumdar, J Therm Anal Calorim. 119 (2015) 885–890 5. A. Aditya Prasad, K. Muthu, M. Rajasekar , V. Meenatchi , SP. Meenakshisundaram , Spectrochim.Acta A , 135 (2015) 46-54. 6. A.Aditya Prasad, K.Muthu, M.Rajasekar, V.Meenatchi, S.P.Meenakshisundaram, Spectrochim. Acta A, 135 (2015) 805-813 7. G. Ramasamy, Subbiah Meenakshisundaram, Optik, 2014(125) 4422-4426 8. S. Sivaraman, C. Balakrishnana, A. Aditya Prasadb, R. M. Sokalingama, S. P. Meenakshisundarama, R. Markkandan, Mol. Cryst. Liq. Cryst. 165(2017)153-168.
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S. Sivaraman et al. / Materials Today: Proceedings 15 (2019) 654–662
9. A. Aditya Prasad, S.Kalainathan, S. P. Meenakshisundaram, Optick, 127(2016) 6134-6149 10. A . Agilandeswari, A. Aditya Prasad, S. Sivaraman, S.Kalainathan, S. P. Meenakshisundaram, Mol. Cryst. Liq. Cryst. 265(2015) 238252 11. Hong-lan Cai, Bing Liu and Qing-an Qiao, Acta Cryst., E70(2014) o15. 12. Xiao-Gang Mu., Xuan- Jun Wang., Youzhi Zhang., Xiaoli Gou., & Xia Li. (2011). Acta Cryst, E67, o3378. 13. 2009M. J. Frisch, G.W. Trucks,. Gaussian 09, Revision C.01, Gaussian, Inc., Wallingford, CT. 2009 14. R.Dennington, T. Keith, J. Millam,. Gauss View, Version 5, Semichem Inc., Shawnee Mission KS. 15. RO. MU. Jauhar, P. Murugakoothan,. AIP Conf. Proc, 1832 (2017)100005. 16. M. A.Spackman, D. Jayatilaka. CrystEngComm, 11(2009)19–32. 17. F. L. Hirshfeld, Theor. Chim. Acta, 44 (1977)129–138. 18. S. K. Wolff, D. J. Grimwood, J. J. McKinnon, M. J. Turner, D. Jayatilaka, M. A. SpackmanCrystalExplorer (Version3.1), University of Western Australia., 2012. 19. Hendry I. Elim, Jian Yang, Jim-Yang Lee, Jun Mi, Wei Ji, Appl. Phys. Lett. 88(2006) 083107 20. He, G. S.; Tan, L. S.; Zheng, Q.; Prasad, P. N. Chem. Rev., 108(2008)1245. 21. Lakshminarayana Polavarapu, Qing-Hua Xu, Mohan S. Dhoni, Wei Ji, Appl. Phys. Lett. 92 (2008) 263110 22. Geok-Kieng Lim, Zhi-Li Chen, Jenny Clark, Roland G. S. Goh, Wee-Hao Ng, Hong-Wee Tan, Richard H. Friend, Peter K. H. Ho, LayLay Chua, Nat.Photonics,5 (2011) 554.