Optical Switching of Azophenol Derivatives in Solution and in Polymer Thin Films: The Role of Chemical Substitution and Environment
American Journal of Nano Research and Applications
Volume 2, Issue 6-1, December 2014, Pages: 39-52
Received: Nov. 16, 2014;
Accepted: Nov. 19, 2014;
Published: Dec. 23, 2014
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Yasser M. Riyad, Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Faculty of Chemistry and Mineralogy, University of Leipzig, Permoserstrasse 15, 04318 Leipzig, Germany; Chemistry Department, Faculty of Science, Al-Azhar University, Nasr City, 11884, Cairo, Egypt
Sergej Naumov, Chemical Department, Leibniz Institute of Surface Modification, Permoserstrasse 15, 04318 Leipzig, Germany
Jan Griebel, Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Faculty of Chemistry and Mineralogy, University of Leipzig, Permoserstrasse 15, 04318 Leipzig, Germany
Christian Elsner, Chemical Department, Leibniz Institute of Surface Modification, Permoserstrasse 15, 04318 Leipzig, Germany
Ralf Hermann, Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Faculty of Chemistry and Mineralogy, University of Leipzig, Permoserstrasse 15, 04318 Leipzig, Germany
Katrin R. Siefermann, Chemical Department, Leibniz Institute of Surface Modification, Permoserstrasse 15, 04318 Leipzig, Germany
Bernd Abel, Chemical Department, Leibniz Institute of Surface Modification, Permoserstrasse 15, 04318 Leipzig, Germany
Design of polymer materials whose properties can be reversibly changed by illumination with light is a technology of particular scientific interest. Such materials contain molecular chromophors, which change their geometry and/or polarity upon absorption of light of a specific wavelength. The most prominent chromophores are azobenzene derivatives. Here, we present a systematic study on azobenzene derivatives in order to quantify the impact of chemical substitution and chemical environment on the dynamics of light-induced trans-cis isomerization (at 368 nm and 355 nm), thermal cis-trans relaxation, and light-induced cis-trans isomerization (at 434 nm). Systems under investigation were 4-hydroxyazobenzene (4-HAB) in acetonitrile (MeCN) solution and in a poly(methylmethacrylate) (PMMA) matrix. These two systems are compared to systems in which 4-HAB is esterified, namely 4-hydroxyazobenzene covalently bound (esterified) to PMMA matrix, and N-(tert-butoxycarbonyl)glycine-4- hydroxyazobenzene (Boc-Gly-4-HAB) in MeCN and in PMMA. Photoisomerization and thermal relaxation kinetics are monitored with UV-vis absorption spectroscopy and accompanied by quantum chemical calculations to shed light into the molecular origin of observed differences in switching properties. We find that the chemical environment (MeCN vs. PMMA) only has minor impacts (~10%) on trans to cis photoisomerization rates. Also, the impact of chemical environment on thermal cis to trans relaxation is small; with relaxation rates in PMMA beeing < 35% smaller compared to rates in MeCN solution. However, the thermal cis to trans relaxation rates of 4-HAB are clearly faster (factor > 400) than the rates of esterified systems. This difference is a clear result of the different substituents on the azobenzene moiety. Quantum chemical calculations suggest that the cis-configuration in the esterified systems is stabilized by an intramolecular H-bond between a carbonyl oxygen on the substituent and an H atom on the phenyl ring. In all systems, the cis to trans isomerization can be significantly accelerated by illumination with 434 nm light. For esterified systems, accelerations by factors of about 5700 – 15500 are observed. In the case of 4-hydroxyazobenzene covalently bound (esterified) to the PMMA matrix, complete light induced transfer from cis to trans is possible. In addition, it features a low thermal cis to trans isomerization rate and acceptable photoinduced trans to cis isomerization properties. With this, the material fulfills the basic requirements of a functional polymer material whose properties can be reversibly changed by illumination with light.
Yasser M. Riyad,
Katrin R. Siefermann,
Optical Switching of Azophenol Derivatives in Solution and in Polymer Thin Films: The Role of Chemical Substitution and Environment, American Journal of Nano Research and Applications. Special Issue: Advanced Functional Materials.
Vol. 2, No. 6-1,
2014, pp. 39-52.
Z. F. Liu, K. Hashimoto, A. Fujishima. Photoelectrochemical information storage using an azobenzene derivative. Nature 1990, 347, 658-660.
T. Ikeda, O. Tsutsumi. Optical switching and image storage by means of azobenzene liquid-crystal films. Science 1995, 268, 1873-1875.
J. W. Brown, B. L. Henderson, M. D. Kiesz, A. C. Whalley, W. Morris, S. Grunder, H. Deng, H. Furukawa, J. I. Zink, J. F. Stoddart, O. M. Yaghi. Photophysical pore control in an azobenzene-containing metal-organic framework. Chem. Sci. 2013, 4, 2858–2864.
J. E. Green, J. W. Choi, A. Boukai, Y. Bunimovich, E. Johnston-Halperin, E. DeIonno, Y. Luo, B. A. Sheriff, K. Xu, Y. Shik Shin, H.-R. Tseng, J. F. Stoddart, J. R. Heath. A 160-kilobit molecular electronic memory patterned at 10(11) bits per square centimetre. Nature 2007, 445, 414–417.
E. Orgiu, N. Crivillers, M. Herder, L. Grubert, M. Pätzel, J. Frisch, E. Pavlica, D. T. Duong, G. Bratina, A. Salleo, N. Koch, S. Hecht, P. Samori. Optically switchable transistor via energy-level phototuning in a bicomponent organic semiconductor. Nat. Chem. 2012, 4, 675–679.
B. Lewandowski, G. De. Bo, J. W. Ward, M. Papmeyer, S. Kuschel, M. J. Aldegunde, P. M. E. Gramlich, D. Heckmann, S. M. Goldup, D. M. D’Souza, A. E. Fernandes, D. A. Leigh. Sequence-Specific Peptide Synthesis by an Artificial Small-Molecule Machine. Science 2013, 339, 189–193.
E. R. Kay, D. A. Leigh, F. Zerbetto. Synthetic molecular motors and mechanical machines. Angew. Chem. Int. Ed. 2007, 46, 72–191.
D. S. Marlin, D. G. Cabrera, D. A. Leigh, A. M. Z. Slawin. An allosterically regulated molecular shuttle. Angew. Chem. Int. Ed. 2006, 45, 1385-1390.
D. A. Leigh, J. K. Y. Wong, F. Dehez, F. Zerbetto. Unidirectional rotation in a mechanically interlocked molecular rotor. Nature 2003, 424, 174-179.
N. Koumura, R. W. J. Zijlstra, R. A. van Delden, N. Harada, B. L. Feringa. Light-driven monodirectional molecular rotor. Nature 1999, 401, 152-155.
A. M. Brouwer, C. Frochot, F. G. Gatti, D. A. Leigh, L. Mottier, F. Paolucci, S. Roffia, G. W. H. Wurpel. Photoinduction of fast, reversible translational motion in a hydrogen-bonded molecular shuttle. Science 2001, 291, 2124-2128.
N. Liu, Z. Chen, D. R. Dunphy, Y.-B. Jiang, R. A. Assink, C. J. Brinker, Photoresponsive nanocomposite formed by self-assembly of an azobenzene-modified silane. Angew. Chem. Int. Ed. 2003, 42, 1731-1734.
C. Zhang, M.-H. Du, H.-P. Cheng, X.-G. Zhang, A. E. Roitberg, J. L. Krause. Coherent electron transport through an azobenzene molecule: A light-driven molecular switch. Phy. Rev. Lett. 2004, 92, 158301/1-158301/4.
W. R. Browne, B. L. Feringa. Making molecular machines work. Nature Nanotech. 2006, 1, 25-35.
S. Muramatsu, K. Kinbara, H. Taguchi, N. Ishii, T. Aida. Semibiological molecular machine with an implemented and logic gate for regulation of protein folding. J. Am. Chem. Soc. 2006, 128, 3764-3769.
I. Willner, S. Rubin. Control of the structure and functions of biomaterials by light. Angew. Chem. Int. Ed. 1996, 35, 367-385.
L. Ulysse, J. Cubillos, J. Chmielewski. Photoregulation of cyclic peptide conformation. J. Am. Chem. Soc., 1995, 117, 8466-8467.
H. Asanuma, X. Liang, T. Yoshida, A. Yamazawa, M. Komiyama. Photocontrol of triple-helix formation by using azobenzene-bearing oligo(thymidine). Angew. Chem. Int. Ed. 2000, 39, 1316-1318.
S. Spörlein, H. Carstens, H. Satzger, C. Renner, R. Behrendt, L. Moroder, P. Tavan, W. Zinth, J. Wachtveitl. Ultrafast spectroscopy reveals subnanosecond peptide conformational dynamics and validates molecular dynamics simulation. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 7998-8002.
X. Liang, H. Asanuma, M. Komiyama. Photoregulation of DNA triplex formation by azobenzene. J. Am. Chem. Soc. 2002, 124, 1877-1883.
G. S. Kumar, D. C. Neckers. Photochemistry of azobenzene-containing polymers. Chem. Rev. 1989, 89, 1915-1925.
T. Hugel, N. B. Holland, A. Cattani, L. Moroder, M. Seitz, H. E. Gaub. Single-molecule optomechanical cycle. Science 2002, 296, 1103-1106.
N. B. Holland, T. Hugel, G. Neuert, A. Cattani-Scholz, C. Renner, D. Oesterhelt, L. Moroder, M. Seitz, H. E. Gaub. Single molecule force spectroscopy of azobenzene polymers: Switching elasticity of single photochromic macromolecules. Macromolecules, 2003, 36, 2015-2023.
A. Natansohn, P. Rochon, Photoinduced motions in azo-containing polymers. Chem. Rev. 2002, 102, 4139-4175.
A. Priimagi, A. Shevchenk, Azopolymer-based micro- and nanopatterning for photonic applications. J. Polym. Sci. Part B: Polym. Phys. 2014, 52, 163–182.
E. Merino, M. Ribagorda, Control over molecular motion using the cis-trans photoisomerization of the azo group. Beilstein. J. Org. Chem. 2012, 8, 1071-1090.
S. Monti, G. Orlandi, P. Palmieri. Features of the photochemically active state surfaces of azobenzene. Chem. Phys. 1982, 71, 87-99.
H. Bouas-Laurent, H. Durr. Organic photochromism. Pure Appl. Chem. 2001, 73, 639–665.
P. D. Wildes, J. G. Pacifici, G. Irick, D. G. Whitten, Solvent and substituent effects on thermal isomerization of substituted azobenzenes. Flash spectroscopic study. J. Am. Chem. Soc. 1971, 93, 2004–2008.
C. S. Paik, H. Morawetz, Photochemical and thermal isomerization of azoaromatic residues in side chains and backbone of polymers in bulk. Macromolecules. 1972, 5: 171–177.
J. M. Nerbonne, R. G. Weiss, Elucidation of thermal-isomerization mechanism for azobenzene in a cholesteric liquid-crystal solvent. J. Am. Chem. Soc. 1978, 100, 5953–5954.
H. J. Haitjema, Y. Y. Tan, G. Challa, Thermal isomerization of azobenzene- based acrylic-monomers and (co)polymers with dimethylamino substituents in solution, influence of addition of (poly)acid, copolymer composition, spacer length, and solvent type. Macromolecules, 1995, 28, 2867–2873.
C. H. Wang, R. G. Weiss, Thermal cis→trans isomerization of covalently attached azobenzene groups in undrawn and drawn polyethylene films. Characterization and comparisons of occupied sites. Macromolecules, 2003, 36, 3833–3840.
D. Acierno, E. Amendola, V. Bugatti, S. Concilio, L. Giorgini, P. Iannelli, S. P. Piotto, Synthesi and characterization of segmented liquid crystalline polymers with the azo group in the main chain. Macromolecules 2004, 37, 6418-6423.
S. L. Sin, L. H. Gan, X. Hu, K. C. Tam, Y. Y. Gan, Photochemical and thermal isomerization of azobenzene-containing amphiphilic diblock copolymers in aqueous micellar aggregates and in film. Macromolecules 2005, 38, 3943-3948.
S. Furumi, K. Ichimura, Effect of para-substituents on azobenzene side chains tethered to poly(methacrylate)s on pretilt angle photocontrol of nematic liquid crystals. Thin Solid Films 2006, 499, 135-142.
P. Sierocki, H. Mass, P. Dragut, G. Richardt, F. Vögtle, L. De Cola, F. A. M. Brouwer, J. I. Zink, Photoisomerization of azobenzene derivatives in nanostructured silica. J. Phys. Chem. B 2006, 110, 24390-24398.
N. A. Wazzan, P. R. Richardson, A. C. Jones, Cis-Trans isomerisation of azobenzenes studied by laser-coupled NMR spectroscopy and DFT calculations. Photochem. Photobiol. Sci. 2010, 9, 968-974.
A. A. Beharry, O. Sadovski, G.A. Woolley. Azobenzene photoswitching without ultraviolet Light. J. Am. Chem. Soc. 2011, 133, 19684-19687.
U. Georgi, P. Reichenbach, U. Oertel, L.M. Eng, B. Voit. Synthesis of azobenzene-containing polymers and investigation of their substituent-dependent isomerisation behavior. React. Funct. Polym. 2012, 72, 242-251.
P. J. Coelho, C. M. Sousa, M. C. R. Castro, A. M. C. Fonseca, M. M. M. Raposo, Fast thermal cis-trans isomerization of heterocyclic azo dyes in PMMA polymers. Opt. Mater., 2013, 35, 1167-1172.
J. Garcia-Amoos, D. Velasco, Understanding the fast thermal isomerization of azophenols in glassy and liquid-crystalline polymers. Phys. Chem. Chem. Phys., 2014, 16, 3108-3114.
J. Garcia-Amoros, D. Velasco. Recent advances towards azobenzene-based light-driven real-time information-transmitting materials. Beilstein J. Org. Chem. 2012, 8, 1003-1017.
J. Garcia-Amoros, D. Velasco. In Responsive Materials and Methods (Advanced Materials Series), ed. A. Tiwari and H. Kobayashi, WILEY-Scrivener Publishing LLC, New Jersey, 2013, chapter 2.
Y. Kishimoto, J. Abe. A fast photochromic molecule that colors only under UV light. J. Am. Chem. Soc. 2009, 131, 4227-4229.
J. Garcia-Amoros, A. Sanchez-Ferrer, W. A. Massad, S. Nonell, D. Velasco. Kinetic study of the fast thermal cis-to-trans isomerisation of para-, ortho- and polyhydroxyazobenzenes. Phys. Chem. Chem. Phys. 2010, 12, 13238-13242.
M. Kojima, S. Nebashi, K. Okawa, N. Kurita. Effect of solvent on cis-to-trans isomerization of 4-hydroxyazobenzene aggregated through intermolecular hydrogen bonds. J. Phys. Org. Chem. 2005, 18, 994-1000.
H. M. D. Bandara, S. C. Burdette. Photoisomerization in different classes of azobenzene. Chem. Soc. Rev. 2012, 41, 1809–1825
A. Altomare, C. Carlini, F. Ciardelli, R. Solaro. Photochromism of 4-Acryloxybenzene/(-)-methyl acrylate copolymers. J. Polym. Sci., Polym. Chem. Ed. 1984, 22, 1267-1280.
A. D. Becke. Density-functional thermochemistry .4. A new dynamical correlation functional and implications for exact-exchange mixing. J. Chem. Phys., 1996,104, 1040-1046.
C. T. Lee, W. T. Yang; R. G. Parr. Development of the colle-salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785-789.
Jaguar, version 8.3, Schrodinger, Inc., New York, NY, 2014.
D. J. M. Tannor, B. Murphy, R. Friesner, R. A. Sitkoff, D. Nicholls, A. Ringnalda, W. A. M. Goddard, III, B. Honig. Charge-distribution and solvation energies from ab-Initio quantum mechanics and continuum dielectric theory. J. Am. Chem. Soc. 1994, 116, 11875-11882.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr. R. E.Stratmann, J. C. Burant, et al. Gaussian 03, Revision A.11, Gaussian, Inc., Pittsburgh PA, 2003.
R. A. Friesner, New methods for electronic structure calculations on large molecules. New methods for electronic-structure calculations on large molecules. Ann. Rev. Phys. Chem. 1991, 42, 341-367.
W. T. Pollard, R. A. Friesner. Efficient Fock matrix diagonalization by a Krylov-space method. J. Chem. Phys. 1993, 99, 6742-6750.
L. Angiolini, D. Caretti, L. Giorgini, E. Sabatelli, A. Altomare, C. Carlini, R. Solaro, Synthesis, chiroptical properties and photoresponsive behaviour of optically active poly[(S)-4-(2-methacryloyloxypropanoyloxy)azobenzene]. Polymer 1998, 39, 6621–6629.
N. K. S. Tanaka, S. Itoh. Ab initio molecular orbital and density functional studies on the stable structures and vibrational properties of trans- and cis-azobenzenes. J. Phys. Chem. A 2000, 104, 8114-8120.
A. A. Blevins, G. J. Blanchard. Effect of positional substitution on the optical response of symmetrically disubstituted azobenzene derivatives. J. Phys. Chem. B 2004, 108, 4962-4968.
L. Wang, C. Yi, H. Zou, J. Xu, W. Xu. Theoretical study on the isomerization mechanisms of phenylazopyridine on S0 and S1 states. J. Phys. Org. Chem. 2009, 22, 888–896.
C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, VCH Verlagsgeselschaft, Weinheim, 1990.