Anomalous Dielectric Features and Structural Implications in Gallic

Page 1 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Anomalous dielectric features and structural implications in Gallic acid-Isoniazid cocrystal mediated by lattice water Ramanpreet Kaur, # Bharathi Ponraj, $ Diptikanta Swain, # K. B. R.Varma, $ Tayur N. Guru Row

#

*

#

Solid State and Structural Chemistry Unit, Indian Institute of Science, Bengaluru 560012, India

$

Materials Research Center, Indian Institute of Science, Bengaluru 560012, India

KEYWORDS: Organic cocrystal/salt, Hydrogen bond, Structural phase transition, Dielectric behaviour.

ABSTRACT: An organic supramolecular ternary salt (gallic acid: isoniazid: water; GINZH) examined earlier for its proton conducting characteristics is observed to display step like dielectric behaviour across the structural phase transition mediated by loss of water of hydration at 389K. The presence of hydration in the crystal lattice along with proton mobility between acid-base pairs controls the “ferroelectric like” behaviour until the phase transition temperature. Research in development of organic molecular systems as functional materials has been of specific interest in recent times. 1 The simplicity, cheap synthesis, flexibility and non-toxic nature

ACS Paragon Plus Environment

1


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 18

of such materials have been highlighted for the design of device applications. 2 In this context, some of the physical properties like dielectric and ferroelectric behaviour 3-12 of such materials have been correlated with their structural features. In particular, considerable attention has been placed on switchable dielectric materials for data storage and data dissemination applications, resulting from the transition between dynamic/disordered phases in molecular solids.5-12 A typical example for a ferroelectric phase generation is seen in the A2BX4 system wherein defects induce pinning in the system.13 Hydrogen bonded ferroelectrics, for example potassium dihydrogen phosphate (KDP),

14,15

have identified the importance of proton dynamics as an

essential prerequisite for generation of spontaneous polarization leading to ferroelectric properties. Even though conventional ceramic and inorganic oxide materials

16,17

have been

explored extensively for dielectric and ferroelectric behaviour, organic-inorganic hybrids and organic materials

21-26

18-20

have recently gained importance. The participation of hydrogen

bonding and its dynamics in cocrystals/salts based on parameters like subtle changes in molecular environment, the pKa values of participating co-formers and temperature control on the proton migration

27-31

indicates that water of hydration might also play a significant role in

tuning physical properties. Recent studies32-34 on the cocrystal of phenazine and chloranilic acid on cooling show an incommensurately modulated ferroelectric phase

resulting due to

competition in proton transfer as against coulomb repulsion. In our earlier studies,35 we have shown that gallic acid

36-38

has a special affinity towards

lattice water and it was surmised that since GINZH is non centrosymmetric, the dielectric/ferroelectric property of this material might be harnessed by the presence or absence of water. It has been shown by us38 that crystallization of gallic acid : isoniazid from 1:1 molar mixture of methanol/water or ethanol/water resulted in a concomitant growth of both hydrated


2

Page 3 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


and anhydrous forms; GINZH (gallic acid : isoniazid : water; Scheme 1) and its anhydrous GINZA respectively. Further, it was demonstrated that GINZH undergoes a single crystal to single crystal transformation (SCSC) to GINZA. Since the GINZH and GINZA belong to a noncentrosymmetric P21 and a centro-symmetric P-1 respectively, a unique model system is on offer to investigate dielectric/ferroelectric behaviour with or without the presence of the water molecule.

Scheme 1. Structural formula of GINZH.

In this article, we have extended our studies to evaluate dielectric/ferroelectric properties in GINZH and in particular to ascertain the controlling ability of lattice water. To the best of our knowledge, this is the first example of multicomponent system (organic cocrystal/salts) in which water molecules play a crucial role to generate a step like dielectric properties along with a ferroelectric like behaviour in tandem. It is of interest to note that even though several articles in literature concerning ferroelectricity display characterstic P-E loops, most of these are indeed leaky dielctrics.39-47 The increase of leakage current with electric field is commensurate with increase in conductivity in many of these reported compounds.39-47 In such cases, additional supporting experiments are conducted 48 to establish the materials as proper ferroelectrics. These experiments include Current versus Electric field (I vs E) characteristics, Positive Up Negative Down (PUND) measurements, which clearly establish the ferroelectric nature of the material.


3


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 18

In the present work, crystals of GINZH and GINZA were prepared concomitantly as described earlier

48

and based on the morphology GINZH was separated and used in the subsequent

experiments. We have earlier reported the crystal structure of both forms and have studied phase transition with temperature. 38 It is to be noted that GINZA obtained concomitantly with GINZH is identical to the anhydrous form obtained by heating GINZH to 389 K. Since the intention of the earlier work 38 was to report the SCSC transition mainly and follow the conductivity features, the exact temperature of phase transition was not clearly identified, though it was made sure that the conversion from GINZH to GINZA is complete by heating to around 423 K before single crystal XRD measurements. Consequently the differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were repeated to carefully monitor the transition temperature (Figure 1) and supporting evidence was sought from specific heat measurements as well (Figure S1; Supporting Information). These experiments suggest the transition to be at 389 K. The endothermic peak in DSC represents the loss of two water molecules (Weight loss=5.43 % from TGA; entropy change = 8.56 JK-1mol-1) and the peaks at 494 K and 514 K correspond to melting and decomposition respectively (Figure 1). Based on Boltzmann equation ∆S=R ln N (where R is the gas constant, the N is the ratio of possible configurations), the value of N is evaluated to be 2.80 corresponding to the process of elimination of the water molecule from GINZH.

Figure 1. (a) DSC and (b) TGA plots of GINZH showing phase transition at 389K.The peaks at 494K and 514K correspond to melting and decomposition respectively.TGA (b) indicates a weight loss of 5.43% corresponds to the removal of two water molecules.


4

Page 5 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


It is well established that the dielectric constant could exhibit an anomaly near structural phase transition temperature. Thus, measurements of the temperature dependent dielectric constant were carried out on powder pressed pellets of GINZH to identify dielectric behaviour in the vicinity of phase transition. The purity of the sample was confirmed by Powder X-ray diffraction profile fitting (Figure S2 (a); Supporting Information). The pellet was subjected to crosssectional SEM before performing physical property measurements which confirmed the dense nature of sample (Figure S2 (b); Supporting Information). Initial measurements of the dielectric constant as a function of frequency were made on GINZH. The value of ɛr at room temperature was around 8 at 100 Hz and it decreases with increase in frequency up to 1 MHz (Figure S3(a); Supporting Information). Correspondingly, the dielectric loss (D) is maximum at lower frequencies and decreases slightly with increase in frequency (Figure S3 (b); Supporting Information). This could be attributed to space charge effect. Figure 2 depicts the temperature dependent dielectric constant at various frequencies (10 kHz, 100 kHz and 1 MHz). Dielectric constant at about 363 K exhibits initiation of a step like behavior towards a lower dielectric state and decreases with increase in frequency. It is of interest to note that above 389 K, the dielectric constant drops to about 5.5 and remains invariant on the cooling cycle due to the loss of the water of hydration (Figure 2 inset). Further, loss of water molecule and irreversibility of transition was also captured by in situ powder X-ray diffraction (Figure S4; Supporting Information).Thus, even though this material does not exhibit switchable dielectric phenomenon 5-12

, the appearance of a step like behavior brings out the role of lattice water initially in

augmenting the value of the dielectric constant.


5


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 18

Figure 2. Temperature dependent step like dielectric constant of GINZH at various frequencies (10 kHz, 100 kHz and 1 MHz) and inset diagram shows irreversibility of the transition in GINZH.

Figure 3a represents the hysteresis curve of polarization (P) vs electric field (E) for GINZH. The hysteresis loop measured at different electric field at frequency of 0.2 Hz (Figure 3a) for room temperature shows that the Pr value increases with increase in electric field having Pr = 0.016 µC/cm2 with Ec = 4.64 kV/cm at 10 kV/cm and increases to Pr = 0.04 µC/cm2 with Ec = 9.79 kV/cm at 20 kV/cm. With further increase in amplitude of applied electric field, polarization increases and similar trend is observed up to maximum field of 64 kV/cm. The hysteresis loop measured at frequencies in the range of 0.2 Hz - 10 Hz (Figure S5; Supporting Information) at 64 kV/cm shows that the Pr value decreases with increase in frequency [Pr = 0.15µC/cm2 with Ec = 29 kV/cm at 0.2 Hz]. This feature is attributed to the contribution of space charge and domain wall motion associated with the sample. The decrease in Pr value to 0.02 µC/cm2 with Ec = 5.9 kV/cm at 10 Hz is due to the delay in switching of domains towards field direction which amounts to a reduction in hysteresis area of the loop. 49,50


6

Page 7 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 3. (a) Hysteresis loop measurements of the polarization (P) versus electric field (E) at different electric field at RT and (b) leakage current versus applied electric field.

The P-E loops do not reach saturation, a feature which is similar to that observed for BiFeO3 and is reasoned to be due to large leakage current.51 In order to evaluate the reasons for increase in the area under the loop with respect to the applied electric field, leakage current with respect to electric field were estimated (Figure 3b). The increase of leakage current with electric field is commensurate with the increase of conductivity in the sample, consistent with that reported in our earlier work. 38 It is of interest to note at this stage that there are several examples 39-47 which display similar P vs E characteristics and the materials are claimed to be ferroelectrics by the authors.


7


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 18

The Current vs. Electric field (I-E) loop allows for the determination of the domain switching peak current if the material is ferroelectric and Figure S6 (Supporting Information) shows no apparent domain switching current. This does not provide a positive proof for the existence of ferroelectricity in the sample. However, it might be surmised that domain switching current peaks could be masked due to the presence of high proton conductivity in the present case. 38, 48 PUND measurements, suggested to be performed on a single crystal, allow for the subtraction of extrinsic contribution arising from leakage current.52 This method contains six consecutive electric field pulses with sufficient delay time. The first two pulses, alternatively positive and negative are given to pole the sample with a defined negative polarized state. Then two consecutive positive pulses are given to the sample which can be called as Positive (P) and Up (P’). The pulse P gives ferroelectric polarization as well as leakage contribution whereas P’ pulse accounts for the leakage contribution. Hence, subtracting P’ from P, gives the ferroelectric polarization for positive electric field. Likewise, by giving two consecutive negative pulses, called as Negative (N) and Down (N’) in which N contains both ferroelectric and leakage contribution while N’ contains only leakage contribution, the difference N-N’ gives the intrinsic ferroelectric contribution for negative field. In the current study on GINZH no change in polarization is observed thus negating the support for this material to be ferroelectric (Figure S7; Supporting Information). Thus the two supporting experiments fail to establish that the material is ferroelectric in a classical sense. It might be argued that the experiments described to attest that a material is a ferroelectric has been limited mostly to inorganic materials and the mechanisms are attributed to be due to presence of dipole inversion units in the respective domains. In an example of the type described in this article, the dipole inversion could only be at the acid-base hydrogen bonded units and


8

Page 9 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


hence the flipping is rather sluggish and hence the saturation in the P vs. E plot could be difficult to attain, particularly with the increase in the leakage current as a consequence of conductivity in the material. Thus, we would suggest that the system displays “ferroelectric like” behaviour. It is indicative that new experiments need to be devised to explore the nature of such materials. Temperature dependent Raman spectroscopy studies have been carried out to obtain insights into the dynamics of structural transition. Figure 4 shows Raman active modes in GINZH and an assignment to each mode is made based on available literature.53 Dramatic changes are seen at the phase transition temperature with (i) disappearance of 1605 cm-1 peak which corresponds to the ionized COO- of gallate ion of GINZH (ii) appearance of 1706 cm-1 peak corresponding to COOH (Figure 4).These changes are consistent with the structural changes observed particularly in the hydrogen bonded regions. An interesting phenomenon has been observed in the C=O of the amide group of isoniazid moiety. The region covering 1630 cm-1 and 1645 cm-1 corresponds to C=O of isoniazid moiety which generally appears at 1650 cm-1 but there is small shift due to hydrogen bonding of amide group. The C=O of the amide group of isoniazid moiety forms hydrogen bonding with water molecule via O-H…O interactions. After transition, C=O interacts with hydroxyl group of gallic acid molecule and there is slight shift to lower frequency i.e.1627 cm-1 and 1643 cm-1.The 1563 cm-1 mode could be arising from the combination of the C-N and N-H in plane bending of the hydrazide group of isoniazid moiety. This mode softens with increasing temperature. After transition the frequency of the mode abruptly decreases and becomes very broad which merge with the background (Figure 4). The interaction of the OH groups of gallic acid with water molecules via O-H···O interactions are indicated with peaks at 1316 cm-1 and 1343 cm-1 representing bending modes of the phenolic group. The removal of the water molecule from the crystal lattice results in the formation of a strong phenolic homodimer,


9


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 18

which causes hardening of these bending modes (Figure S8 (a); Supporting Information). The transition also produces recognizable changes in the peak position in the region of 700-900 cm-1 (Figure S8 (b); Supporting Information).

Figure 4. Temperature evolution of Raman bands in GINZH in region corresponding to 1500-1750 cm-1 confirming the phase transition.

Comparison of the crystal structures of GINZH (RT phase) and GINZA (HT phase) confirms the transition with the lowering of symmetry (from P21 to P-1) with the loss of two water molecules from the crystal lattice. The relevance of the strength of the hydrogen bond formed between participating molecules in a cocrystal has been evaluated critically using both neutron and synchrotron diffraction by Tokura and co-workers.54,55 In case of GINZH which represents gallic acid and isoniazid; the proton affinity is nearly same56,57 and as a consequence location of proton becomes ambiguous on based of X-ray diffraction data. However, the geometrical factors associated with the hydrogen bonding provide sufficient clue to the location of the proton. Difference Fourier analysis places the proton nearly halfway between the N and O atom38 in


10

Page 11 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


agreement with the mechanism proposed by Tokura et.al.58,59 resulting in GINZH to depict dielectric/ferroelectric like behaviour. Based on mechanism proposed, the change in C-O bond length [from 1.291 Å and 1.299 Å (GINZH) to 1.327 and1.336 Å (GINZA) for two acid molecules] followed by reduction of C=N-C bond angles [from 119.95 ͦ and 121.29 ͦ (GINZH) to 117.8 ͦ and 118.1 ͦ (GINZA) for two isoniazid molecules in an asymmetric unit)] suggests that the hydrogen bonding might posses an ionic character in GINZH. Figure 5 brings out the structural reasoning for the step like behaviour in the dielectric response. The gradual increase in N···O bond distance with increase in temperature is consistent with the position of the proton. The proton migrates towards the acid and with the removal of water molecule at 389 K, the COO- moiety of gallate ion results in COOH formation forming gallic acid and consequently a dramatic decrease is observed in the value of the dielectric constant. From structural point of view, the water molecule which resides on the 21 screw axis gets removed and the participating acid-base groups form exclusively phenolic homodimers. It is of interest to note that the packing of the molecules still retain a pseudo 21 axis (Figure 5). Thus, in GINZH, it is obvious that the presence of water of hydration on the 21 screw axis keeps the gallic acid and isoniazid organized to possess a hydrogen bond48 with the proton residing approximately at mid point. It would be worthwhile to investigate this phenomenon in detail with neutron diffraction studies.


11


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 18

Figure 5. Hydrogen bonding and displacement of proton position with temperature in GINZH (bold line in green colour illustrates the presence of 21 screw axis in GINZH and dashed line shows the presence of pseudo 21 screw axis in GINZA).

In summary, the concomitant growth of GINZH and GINZA and the subsequent SCSC transition has provided a model system to establish and evaluate the role of lattice water in monitoring the anomalous dielectric and “ferroelectric like” behaviour in the system. The study leads to the design features of organic materials modulated by the presence /absence of lattice water. It is of importance to note that the water molecules in this model system produce long range effects associated with proton migration in participating co-formers suggesting a prerequisite for the design of a functional material. It may be appropriate to mention that new confirmatory experiments need to be developed to establish and utilize the “ferroelectric like” behaviour in such materials. Supporting Information. Experimental Section, Specific heat, PXRD, SEM image, Frequency dependent dielectric constant and loss at RT, P-E hysteresis loop, I-E loop, PUND measurement


12

Page 13 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


and Raman spectra. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author T. N. Guru Row Solid state and Structural Chemistry Unit, Indian Institute of Science, Bengaluru 560012, India. E-mail: [email protected]; Fax: +91-080-23601310; Tel: +91-080-22932796 ACKNOWLEDGMENTS We thank Prof. Rajeev Ranjan, Dr. Brejesh and Mr. Deepak from Department of Material Engineering, IISc, Bangalore and Prof. Sundaresan and Mr. Chandan from JNCASR, Bangalore for useful discussion and their help in P-E loop, PUND measurements. TNGR thanks DST for J.C. Bose fellowship.

REFERENCES 1. Farchioni, R.; Grosso, G.; Organic Electronic Materials: Conjugated Polymers and Low Molecular Weight Organic Solids, Springer, Berlin 2001. 2.

Forrest, S. R. Nature 2004, 428, 911-918.

3. Horiuchi , S.; Tokura, Y. Nat. Mater. 2008, 7, 357-366 and references therein. 4. Tayi, A. S.; Kaeser, A.; Matsumoto, M.; Aida, T.; Stupp, S. I. Nat. Chem. 2015, 7, 281294.


13


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 18

5. Gao, K.; Gu, M.; Qiu, X.; Ying, X. N.; Ye, H. -Y.; Zhang,Yi.; Sun, J.; Meng, X.; Zhang, F. M.; Wu, D.; Cai , H.-L.; Wu , X.S. J. Mater. Chem. C 2014, 2, 9957-9963. 6. Zhang, W.; Ye, H. -Y.; Graf, R.; Spiess, H. W.; Yao, Y.-F.; Zhu, R.-Q.; Xiong, R.-G. J. Am. Chem. Soc. 2013, 135, 5230-5233. 7. Sun , Z.; Luo , J.; Chen , T.; Li , L.; Xiong, R.-G.; Tong, M.-L.; Hong , M. Adv. Funct. Mater. 2012, 22, 4855-4861. 8. Shang, R.; Wang, Z.-M.; Gao, S. Angew. Chem. Int. Ed. 2015, 54, 2534-2537. 9. Zhang, X.; Shao, X. -D.; Li, S. -C.; Cai, Y.; Yao, Y. -F.; Xiong, R. -G.; Zhang, W. Chem. Commun. 2015, 51, 4568-4571. 10. Zhang, Y.; Liao, W. -Q.; Ye, H. -Y.; Fu, D. -W.; Xiong, R. -G. Cryst. Growth Des. 2013, 13, 4025-4030. 11. Shi, P. -P.; Ye, Q.; Li, Q.; Wang, H. -T.; Fu, D. -W.; Zhang, Y.; Xiong, R. -G. Dalton Trans. 2015, 44, 8221-8231 12. Ji, C.; Sun, Z.; Zhang, S. -Q.; Chen, T.; Zhou, P.; Tang, Y.; Zhaoa, S.; Luo, J. J. Mater. Chem. C 2014, 2, 6134-6139. 13. Hamano, K.; Ema, K.; Hirotsu, S. Ferroelecrrics 1981, 36, 343-346. 14. Lines, M. E; Glass, A. M. Principles and Applications of Ferroelectrics and Related Materials, Oxford Univ. Press, Oxford, 1977. 15. Busch, G.; Scherrer, P. Naturwiss. 1935, 23, 737. 16. Haertling, G.H. J. Am. Ceram. Soc. 1999, 4,797-818. 17. Long, X. F.; Ye, Z. G. Chem. Mater. 2007, 19, 1285-1289. 18.Ye, H. Y.; Fu, D. W.; Zhang, Y.; Zhang, W.; Xiong, R. -G.; Huang, S. D. J. Am. Chem. Soc. 2009, 131, 42-43.


14

Page 15 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


19. Ye, H. -Y.; Zhang, Y.; Fu, D. -W.; Xiong, R. -G. Angew. Chem. Int. Ed. 2014, 53, 67246729. 20. Shi, P. -P.; Ye, Q.; Li, Q.; Wang, H. -T.; Fu, D. -W.; Zhang, Y.; Xiong, R. -G. Chem. Mater. 2014, 26, 6042-6049. 21. Kobayashi, K.; Horiuchi, S.; Ishibashi, S.; Kagawa, F.; Murakami, Y.; Kumai, R. Chem. Eur. J. 2014, 20, 17515-17522. 22. Tayi, A. S.; Shveyd, A. K.; Sue, A. C. -H.; Szarko, J. M.; Rolczynski, B. S.; Cao, D.; Kennedy, T. J.; Sarjeant, A. A.; Stern, C. L.; Paxton, W. F.; Wu, W.; dey, S. K.; Fahrenbach, A. C.; Guest, J. R.; Mohseni, H.; Chen, L. X.; Wang, K. L.; Stoddart, J. F.; Stupp, S. I. Nature 2012, 488, 485-489. 23. Zhou, P.; Sun, Z.; Zhang, S.; Chen, T.; Ji, C.; Zhao, S.; Luo, J. Chem. Asian J. 2014, 9, 9961000. 24. Sun, Z.; Chen, T.; Luo, J.; Hong, M. Angew. Chem. Int. Ed. 2012, 51, 3871-3876. 25. Horiuchi, S.; Kumai, R.; Tokura, Y. J. Am. Chem. Soc. 2013, 135, 4492-4500. 26. Zhang, Y.; Ye, H. -Y.; Fu, D. -W.; Xiong, R. -G. Angew. Chem. Int. Ed. 2014, 53, 21142118. 27. Steiner, T.; Wilson, C. C.; Majerz, I. Chem. Commun. 2000, 1231-1232. 28. Steiner, T.; Majerz, I.; Wilson, C. C. Angew. Chem. Int. Ed. 2001, 40, 2651-2654. 29. Cowan, J. A.; Howard, J. A. K.; McIntyre, G. J.; Lo, S. M. -F.; Williams, I. D. Acta Cryst. 2003, B59, 794-801. 30. Parkin, A.; Harte, S. M.; Goeta, A. E.; Wilson, C. C. New J. Chem. 2004, 28, 718-721. 31. Grobelny, P.; Mukherjee, A.; Desiraju, G. R. CrystEngComm 2011, 13, 4358-4364. 32. Smaalen, S. V. Cryst. Rev. 1995, 4, 19-202.


15


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 18

33. Noohinejad, L.; Mondal, S.; Wölfel, A.; Ali, S. I.; Schönleber, A.; Smaalen, S. V. J. Chem. Crystallogr. 2014, 44, 387-393. 34. Noohinejad, L.; Mondal, S.; Ali, S. I.; Dey, S.; Smaalen, S. V.; Schönleber, A. Acta Cryst. 2015, B71, 228-234. 35. Thomas, S. P.; Kaur, R.; Kaur, J.; Sankolli, R.; Nayak, S. K.; Row, T. N. G. J. Mol. Struct. 2013, 1032, 88-92. 36. Clarke, D.; Arora, K. K.; Wojtas, L.; Zaworotko, M. J. Cryst. Growth Des. 2011, 11, 964966. 37. Braun, D. E.; Bhardwaj, R. M.; Florence, A. J.; Tocher, D.A.; Price, S. L. Cryst. Growth Des. 2013, 13, 19-23. 38. Kaur, R.; Perumal, S. S. R. R.; Bhattacharyya, A. J.; Yashonath, S.; Row, T. N. G. Cryst. Growth Des. 2014, 14, 423-426. 39. Asthana, D.; Kumar, A.; Pathak, A.; Sukul, P. K.; Malik, S.; Chatterjee, R.; Patnaik, S.; Rissanene, K.; Mukhopadhyay, P. Chem. Commun. 2011, 47, 8928-8930. 40. Zhou, W. -W.; Chen, J. -T.; Xu, G.; Wang, M. -S.; Zou, J. -P.; Long, X. -F.; Wang, G. -J.; Guo, G. -C.; Huang, J. -S. Chem. Commun. 2008, 2762-2764. 41.Ye, Q.; Song, Y. -M.; Wang, G. -X.; Chen, K.; Fu, D. -W.; Chan, P. W. H.; Zhu, J. -S.; Huang, S. D.; Xiong, R. -G. J. Am. Chem. Soc. 2006, 128, 6554-6555. 42. Tang, Y. -Z.; Yu, Y. -M.; Tan, Y. -H.; Wu, J. -S.; Xiong, J. -B.; Wen, H. -R. Dalton Trans. 2013, 42, 10106-10111. 43. Sui, Y.; Liu, D. -S.; Hu, R. -H.; Chen, H. -M. J. Mater. Chem. 2011, 21, 14599-14603. 44. Xu, G.; Li, Y.; Zhou, W. -W.; Wang, G. -J.; Long, X. -F.; Cai, L. -Z.; Wang, M. -S.; Guo, G. -C.; Huang, J. -S.; Bator, G.; Jakubas, R. J. Mater. Chem. 2009, 19, 2179-218.


16

Page 17 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


45. Fu, D. -W.; W. Z., Xiong, R. -G. Dalton Trans. 2008, 3946-3948. 46. Lin, J. -D.; Long, X. -F.; Lin, P.; Du, S. -W. Cryst. Growth Des. 2010, 10,146-157. 47. Du, F.; Zhang, H.; Tian, C.; Du, S. Cryst. Growth Des. 2013, 13, 1736-1742. 48. Yan, H.; Inam, F.; Viola, G.; Ning, H.; Zhang, H.; Jiang, Q.; Zeng, T.; Gao, Z.; Reece, M. J. J. Adv. Dielect. 2011, 1,107-118. 49. Sekhar, K. C.; Nath, R. J. Appl. Phys. 2007, 102, 044114-044114-7. 50. Reynaerts, C.; De Vos, A. J. Phys. D: Appl. Phys. 1989, 22, 1504-1507. 51. Pradhan, A. K.; Kai Zhang; Hunter, D.; Dadson, J. B.; Loiutts, G. B.; Bhattacharya, P.; Katiyar, R.; Zhang, J.; Sellmyer, D. J.; Roy, U. N.; Cui, Y.; Burger, A. J. Appl. Phys. 2005, 97, 093903-093903-4. 52. Fukunaga M. and Noda, Y. J. Phys. Soc. Jpn. 2008, 77, 064706. 53. Mayo, D. W.; Miller, F. A.; Hannah, R. W. Course notes on the interpretation of Infrared and Raman, Wiley-VCH, 2003. 54. Horiuchi, S.; Ishii, F.; Kumai, R.; Okimoto, Y.; Tachibana, H.; Nagaosa, N.; Tokura, Y. Nat. Mater. 2005, 4, 163-166. 55. Kumai, R.; Horiuchi, S.; Sagayama, H.; Arima, T. -H.; Watanabe, M.; Noda, Y.; Tokura,Y. J. Am. Chem. Soc. 2007, 129, 12920-12921. 56. Becker, C.; Dressman, J. B.; Amidon, G. L.; Junginer, H. E.; MIidha, S.; Kopp K. K. and Shah, V. P. J. Pharm. Sci. 2007, 96, 522-531. 57. Lide, D. R.; C R C Handbook of Chemistry and Physics, 90th ed. (CD-ROM Version 2010); CRC Press/Taylor and Francis: Boca Raton, FL. 58. Horiuchi, S.; Kumai, R.; Tokura, Y. J. Mater. Chem. 2009, 19, 4421-4434. 59. Horiuchi, S.; Kumai R. and Tokura, Y. Angew. Chem. Int. Ed. 2007, 46, 3497-3501.


17


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 18

Graphical abstract

Anomalous dielectric features and structural implications in Gallic acid-Isoniazid cocrystal mediated by lattice water Ramanpreet Kaur, # Bharathi Ponraj, Row #

#

$

Diptikanta Swain, # K. B. R.Varma, $ Tayur N. Guru

*

Solid State and Structural Chemistry Unit, Indian Institute of Science, Bengaluru 560 012,

India $

Materials Research Center, Indian Institute of Science, Bengaluru 560 012, India

A step like dielectric behaviour is observed in a concomitant growth of a gallic acid: isoniazid: water ternary system and the role of water mediation is analyzed with respect to the structural phase transition.


18

Anomalous Dielectric Features and Structural Implications in Gallic

Recommend Documents