Synthesis, Mesomorphic and Computational Characterizations of Nematogenic Schiff Base Derivatives in Pure and Mixed State
Abstract
:1. Introduction
2. Results and Discussion
2.1. Mesomorphic Characterizations
2.2. DFT Calculations
2.2.1. Geometrical Simulations and Thermal Parameters
2.2.2. Frontier Molecular Orbitals (FMOs)
2.2.3. Molecular Electrostatic Potential (MEP)
2.3. Binary Mixture
3. Experiment
Synthesis
4. Conclusions
- Independent on the terminal alkoxy chain length, all synthesized groups (An) are monomorphic exhibiting enantiotropic wide nematic thermal stability.
- The structural parameters, dipole moment and the polarizability of the present compounds are highly affected by the length of the attached terminal flexible chain as well as the N atom in the heterocyclic terminal ring.
- Binary phase diagrams constructed between different homologs showed to possess low melting temperature with wide N mesophase at the eutectic composition.
- The different extent of the physical and structural parameters are sharing together to impact the N temperature range and the thermal stability of present compounds in their pure and mixed states.
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
- Reyes, C.G.; Sharma, A.; Lagerwall, J.P.F. Non-electronic gas sensors from electrospun mats of liquid crystal core fibres for detecting volatile organic compounds at room temperature. Liq. Cryst. 2016, 43, 1986–2001. [Google Scholar] [CrossRef]
- Setia, S.; Sidiq, S.; De, J.; Pani, I.; Pal, S.K. Applications of liquid crystals in biosensing and organic light-emitting devices: Future aspects. Liq. Cryst. 2016, 43, 2009–2050. [Google Scholar] [CrossRef]
- Gupta, R.K.; Manjuladevi, V.; Karthik, C.; Choudhary, K. Thin films of discotic liquid crystals and their applications. Liq. Cryst. 2016, 43, 2079–2091. [Google Scholar] [CrossRef]
- Dong, S.; Zhang, K.; ** nonmesogenic component into mesogenic esters. Mol. Cryst. Liq. Cryst. 2003, 392, 83–95. [Google Scholar] [CrossRef]
- Vora, R.; Gupta, R.; Patel, K. Exhibition of induced mesophases in the binary systems where one or both the components are non-mesogenic. Mol. Cryst. Liq. Cryst. 1991, 209, 251–263. [Google Scholar] [CrossRef]
- Fujimura, S.; Yamamura, Y.; Hishida, M.; Nagatomo, S.; Saito, K. Reentrant nematic phase in 4-alkyl-4′-cyanobiphenyl (nCB) binary mixtures. Liq. Cryst. 2014, 41, 927–932. [Google Scholar] [CrossRef]
- Prasad, A.; Das, M.K. Determination of elastic constants of a binary system (7CPB+ CN) showing nematic, induced smectic Ad and re-entrant nematic phases. Liq. Cryst. 2014, 41, 1261–1268. [Google Scholar] [CrossRef]
- Hogan, J.L.; Imrie, C.T.; Luckhurst, G.R. Asymmetric dimeric liquidcrystals—The preparation and properties of the al-pha-(4-cyanobiphenyl-40-oxy)-omega-(4-normal-alkylanilinebenzylidene-40- oxy)hexanes. Liq. Cryst. 1988, 3, 645–650. [Google Scholar] [CrossRef]
- Attard, G.S.; Date, R.W.; Imrie, C.T.; Luckhurst, G.R.; Roskilly, S.J.; Seddon, J.M.; Taylor, L. Nonsymmetrical dimeric liq-uid-crystals—the preparation and properties of the al-pha-(4-cyanobiphenyl-40-yloxy)-omega-(4-n-alkylanilinebenzylidene-40-oxy) alkanes. Liq. Cryst. 1994, 16, 529–581. [Google Scholar] [CrossRef]
- Imrie, C.T. Non-symmetric liquid crystal dimers: How to make molecules intercalate. Liq. Cryst. 2006, 33, 1449–1485. [Google Scholar] [CrossRef]
- Imrie, C.T.; Henderson, P.A.; Seddon, J.M. Non-symmetric liquid crystal trimers. First example triply-intercalated alternating smectic C phase. J. Mater. Chem. 2004, 14, 2486–2488. [Google Scholar] [CrossRef]
- Alhaddad, O.A.; Ahmed, H.A.; Hagar, M.; Saad, G.R.; Abu Al-Ola, K.A.; Naoum, M.M. Thermal and Photophysical Studies of Binary Mixtures of Liquid Crystal with Different Geometrical Mesogens. Crystals 2020, 10, 223. [Google Scholar] [CrossRef] [Green Version]
- Alnoman, R.B.; Hagar, M.; Ahmed, H.A.; Naoum, M.M.; Sobaih, H.A.; Almshaly, J.S.; Haddad, M.M.; Alhaisoni, R.A.; Alsobhi, T.A. Binary Liquid Crystal Mixtures Based on Schiff Base Derivatives with Oriented Lateral Substituents. Crystals 2020, 10, 319. [Google Scholar] [CrossRef]
- Al-Mutabagani, L.A.; Alshabanah, L.A.; Ahmed, H.A.; Hagar, M.; Al-Ola, K.A.A. New symmetrical U-and wavy-shaped supramolecular H-bonded systems; geometrical and mesomorphic approaches. Molecules 2020, 25, 1420. [Google Scholar] [CrossRef] [Green Version]
- Dave, J.S.; Menon, M. Azomesogens with a heterocyclic moiety. Bull. Mater. Sci. 2000, 23, 237–238. [Google Scholar] [CrossRef]
- Naoum, M.M.; Fahmi, A.A.; Ahmed, N.H.; Saad, G.R. The e_ect of lateral methyl substitution on the mesophase behaviour of aryl 4-alkoxyphenylazo benzoates. Liq. Cryst. 2015, 42, 1627–1637. [Google Scholar]
- Imrie, C.T.; Taylor, L. The preparation and properties of low molar mass liquid crystals possessing lateral alkyl chains. Liq. Cryst. 1989, 6, 1–10. [Google Scholar] [CrossRef]
- Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Pople, J.A. Gaussian 98, Revision a. 7, Gaussian; Gaussian, Inc.: Wallingford, CT, USA, 1998; Volume 12. [Google Scholar]
- Ahmed, H.A.; Hagar, M.; Alhaddad, O.A. New chair shaped supramolecular complexes-based aryl nicotinate derivative; mesomorphic properties and DFT molecular geometry. RSC Adv. 2019, 9, 16366–16374. [Google Scholar] [CrossRef] [Green Version]
- Walker, R.; Pociecha, D.; Strachan, G.J.; Storey, J.M.D.; Gorecka, E.; Imrie, C.T. Molecular curvature, specific intermolecular in-teractions and the twist-bend nematic phase: The synthesis and characterisation of the 1-(4-cyanobiphenyl-4-yl)-6-(4 al-kylanilinebenzylidene-4-oxy)hexanes (CB6O.m). Soft Matter 2019, 15, 3188–3197. [Google Scholar] [CrossRef] [Green Version]
- Elshakre, M.E.; Alalawy, H.H.; Awad, M.I.; El-Anadouli, B.E. On the role of the electronic states of corrosion inhibitors: Quantum chemical-electrochemical correlation study on urea derivatives. Corros. Sci. 2017, 124, 121–130. [Google Scholar] [CrossRef]
Sample Availability: Samples of the compounds An are available from the authors. |
Comp. | TCr-N | ΔHCr-N | TN-I | ΔHN-I | ΔSN-I | ΔT |
---|---|---|---|---|---|---|
A6 | 130.4 | 37.59 | 184.5 | 1.94 | 0.51 | 54.10 |
A8 | 128.6 | 43.40 | 174.2 | 1.80 | 0.48 | 45.60 |
A16 | 122.2 | 55.25 | 146.6 | 1.66 | 0.48 | 24.40 |
Comp. | ZPE, kcal/mol | Thermal Energy, kcal/mol | Enthalpy, kcal/mol | Gibb’s Free Energy, kcal/mol | Entropy, cal/molK |
---|---|---|---|---|---|
A6 | 288.066 | 305.566 | 306.158 | 247.348 | 197.254 |
A8 | 323.766 | 342.923 | 343.515 | 280.483 | 211.414 |
A16 | 466.039 | 492.042 | 492.635 | 412.108 | 270.094 |
Comp. | EHOMO, eV | ELUMO, eV | ∆E, eV | I.E, eV | E.A, eV | Dipole Moment, Debye | Polarizability, Bohr |
---|---|---|---|---|---|---|---|
A6 | −5.669 | −2.097 | 3.572 | 5.669 | 2.097 | 0.896 | 354.830 |
A8 | −5.667 | −2.096 | 3.571 | 5.667 | 2.096 | 0.911 | 379.780 |
A16 | −5.664 | −2.079 | 3.586 | 5.664 | 2.079 | 0.800 | 477.790 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Al-Mutabagani, L.A.; Alshabanah, L.A.; Ahmed, H.A.; Alalawy, H.H.; Al alwani, M.H. Synthesis, Mesomorphic and Computational Characterizations of Nematogenic Schiff Base Derivatives in Pure and Mixed State. Molecules 2021, 26, 2038. https://doi.org/10.3390/molecules26072038
Al-Mutabagani LA, Alshabanah LA, Ahmed HA, Alalawy HH, Al alwani MH. Synthesis, Mesomorphic and Computational Characterizations of Nematogenic Schiff Base Derivatives in Pure and Mixed State. Molecules. 2021; 26(7):2038. https://doi.org/10.3390/molecules26072038
Chicago/Turabian StyleAl-Mutabagani, Laila A., Latifah A. Alshabanah, Hoda A. Ahmed, Hafsa H. Alalawy, and Mayada H. Al alwani. 2021. "Synthesis, Mesomorphic and Computational Characterizations of Nematogenic Schiff Base Derivatives in Pure and Mixed State" Molecules 26, no. 7: 2038. https://doi.org/10.3390/molecules26072038