Abstract
The third-order nonlinear optical (NLO) materials with stimuli-responsive properties have received extraordinary attention due to their controllable photophysical properties. In this work, two attractive metal complexes third-order NLO switches, which are far superior to congeneric optical switches in terms of their performance conversion, versatility, and fast response, were successfully designed and synthesized. The test of their third-order NLO properties proves that the metal complexes exhibit reverse saturable absorption and self-defocusing refraction. After light irradiation, the third-order NLO behavior turns quickly into self-focusing refraction. The relation between the molecular structures and the third-order NLO properties was investigated via1H nuclear magnetic resonance and ultraviolet-visible absorption. The results show that the metal ions have a significant influence on the NLO behavior and reveal the origin of third-order NLO properties via Z-scan determinations, pump-probe technology, and density functional theory calculations. These metal complexes can be used as third-order NLO switches with excellent fatigue resistance and broaden the application range of third-order NLO materials with adjustable performances.
摘要
具有刺激响应性的三阶非线性光学材料由于其可控的光物理性质而受到了广泛的关注. 本文设计并合成了两种少见的金属配合物三阶非线性光开关, 它们在性能转换、 多功能性和响应速度等方面远优于同类光开关材料. 三阶非线性光学性能测试结果表明, 该金属配合物在光照前同时具有反饱和吸收和自散焦折射行为. 而在光照后, 吸收行为立即消失且自散焦折射行为迅速转变为自聚焦折射. 我们利用核磁共振技术和紫外可见吸收光谱研究了分子结构和三阶非线性光学性能之间的关系并探究了金属离子对三阶非线性光学行为产生的影响. 此外, 我们还通过泵浦探测技术和密度泛函理论计算揭示了金属配合物的非线性光学性能产生的机制. 总之, 这两种金属配合物不仅可以作为理想的三阶非线性光开关材料, 而且也能够扩展具有可调节三阶非线性光学性能材料的应用范围.
Article PDF
Similar content being viewed by others
References
Biswal BP, Valligatla S, Wang M, et al. Nonlinear optical switching in regioregular porphyrin covalent organic frameworks. Angew Chem Int Ed, 2019, 58: 6896–6900
Castet F, Rodriguez V, Pozzo JL, et al. Design and characterization of molecular nonlinear optical switches. Acc Chem Res, 2013, 46: 2656–2665
Huang J, Guo S, Zhang Z, et al. Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides. Sci China Mater, 2019, 62: 1798–1806
Samoc M, Gauthier N, Cifuentes MP, et al. Electrochemical switching of the cubic nonlinear optical properties of an aryldiethynyl-linked heterobimetallic complex between three distinct states. Angew Chem Int Ed, 2006, 45: 7376–7379
Aubert V, Guerchais V, Ishow E, et al. Efficient photoswitching of the nonlinear optical properties of dipolar photochromic zinc(II) complexes. Angew Chem Int Ed, 2008, 47: 577–580
Boixel J, Guerchais V, Le Bozec H, et al. Second-order NLO switches from molecules to polymer films based on photochromic cyclometalated platinum(II) complexes. J Am Chem Soc, 2014, 136: 5367–5375
Nitadori H, Ordronneau L, Boixel J, et al. Photoswitching of the second-order nonlinearity of a tetrahedral octupolar multi DTE-based copper(I) complex. Chem Commun, 2012, 48: 10395–10397
Shi Z, Qin L, Zheng H. A second-order nonlinear optical material with a 5-fold interpenetrating diamondoid framework based on two achiral precursors: spontaneous resolution to absolute chiral induction. Dalton Trans, 2017, 46: 4589–4594
Xing XS, Sa RJ, Li PX, et al. Second-order nonlinear optical switching with a record-high contrast for a photochromic and thermochromic bistable crystal. Chem Sci, 2017, 8: 7751–7757
Barlow S, Brédas JL, Getmanenko YA, et al. Polymethine materials with solid-state third-order optical susceptibilities suitable for all-optical signal-processing applications. Mater Horiz, 2014, 1: 577–581
Gieseking RLM. Third-order nonlinear optical properties of Ag nanoclusters: Connecting molecule-like and nanoparticle-like behavior. Chem Mater, 2019, 31: 6850–6859
Gulino A, Compagnini G, Scalisi AA. Large third-order nonlinear optical properties of cadmium oxide thin films. Chem Mater, 2003, 15: 3332–3336
Hales JM, Matichak J, Barlow S, et al. Design of polymethine dyes with large third-order optical nonlinearities and loss figures of merit. Science, 2010, 327: 1485–1488
Jia J, Zhang J, Zhou C, et al. Extended n-conjugated quinazolinone derivatives with enhanced third-order nonlinear optical response. Dyes Pigments, 2019, 166: 314–322
Traber B, Wolff JJ, Rominger F, et al. Hexasubstituted donor-acceptor benzenes as nonlinear optically active molecules with multiple charge-transfer transitions. Chem Eur J, 2004, 10: 1227–1238
Xing C, Liu J, Chen F, et al. Diphenyl-1-pyrenylphosphine: Phototriggered AIE/ACQ transition with remarkable third-order nonlinear optical signal change. Chem Commun, 2020, 56: 4220–4223
Liang X, Zhang Q. Recent progress on intramolecular chargetransfer compounds as photoelectric active materials. Sci China Mater, 2017, 60: 1093–1101
Yin W, Tao C, Wang F, et al. Tuning optical properties of MOF-based thin films by changing the ligands of MOFs. Sci China Mater, 2017, 61: 391–400
Yue Y, Grusenmeyer T, Ma Z, et al. Full-electron ligand-to-ligand charge transfer in a compact Re(I) complex. J Phys Chem A, 2014, 118: 10407–10415
Hou H, Wei Y, Song Y, et al. Metal ions play different roles in the third-order nonlinear optical properties of d10 metal-organic clusters. Angew Chem Int Ed, 2005, 44: 6067–6074
Kulyk B, Guichaoua D, Ayadi A, et al. Functionalized azo-based iminopyridine rhenium complexes for nonlinear optical performance. Dyes Pigments, 2017, 145: 256–262
Wang HY, Jing LX, Wang HQ, et al. Improving the NLO response of bis-cyclometalated iridium(III) complexes by modifying ligands: A DFT study. J Organomet Chem, 2018, 869: 18–25
Chen QF, Zhao X, Liu Q, et al. Tungsten(VI)-copper(I)-sulfur cluster-supported metal-organic frameworks bridged by in situ click-formed tetrazolate ligands. Inorg Chem, 2017, 56: 5669–5679
Chen X, Li HX, Zhang ZY, et al. Activation and amplification of the third-order NLO and luminescent responses of a precursor cluster by a supramolecular approach. Chem Commun, 2012, 48: 4480
Wei ZH, Ni CY, Li HX, et al. [PyH][{TpMo(μ3-S)4Cu3}4(μ12-I)]: A unique tetracubane cluster derived from the S-S bond cleavage and the iodide template effects and its enhanced NLO performances. Chem Commun, 2013, 49: 4836–4838
Zhang WH, Ren ZG, Lang JP. Rational construction of functional molybdenum (tungsten)-copper-sulfur coordination oligomers and polymers from preformed cluster precursors. Chem Soc Rev, 2016, 45: 4995–5019
Qiu XT, Yao R, Zhou WF, et al. Rectangle and [2]catenane from cluster modular construction. Chem Commun, 2018, 54: 4168–4171
Chen Z, Dong S, Zhong C, et al. Photoswitching of the third-order nonlinear optical properties of azobenzene-containing phthalocyanines based on reversible host-guest interactions. J Photochem Photobiol A-Chem, 2009, 206: 213–219
Feng Q, Li Y, Shi G, et al. A photo-controllable third-order nonlinear optical (NLO) switch based on a rhodamine B salicylaldehyde hydrazone metal complex. J Mater Chem C, 2016, 4: 8552–8558
Ordronneau L, Aubert V, Guerchais V, et al. The first hexadithienylethene-substituted tris(bipyridine)metal complexes as quadratic NLO photoswitches: Combined experimental and DFT studies. Chem Eur J, 2013, 19: 5845–5849
Wang HQ, Wang L, Ye JT, et al. Planar octagonal tetranuclear cobaltacarborane macrocycle [(η5-C5 Me5)Co(2,3-Et2C2B4H3-5-C-C-7-C-C)]4 for 2D nonlinear optics: Ultra-high-response and multistate controlled cubic NLO switch. J Phys Chem C, 2017, 121: 28462–28474
Wu X, Xiao J, Sun R, et al. Spindle-type conjugated compounds containing twistacene unit: Synthesis and ultrafast broadband reverse saturable absorption. Adv Opt Mater, 2017, 5: 1600712
Ouyang H, Zhang C, Liu Q, et al. Polarization-tunable nonlinear absorption patterns from saturated absorption to reverse saturated absorption in anisotropic GeS flake and an application of all-optical switching. Sci China Mater, 2020, 63: 1489–1502
Cabré G, Garrido-Charles A, Moreno M, et al. Rationally designed azobenzene photoswitches for efficient two-photon neuronal excitation. Nat Commun, 2019, 10: 907
Xie Y, Fu D, Jin O, et al. Photoswitchable molecular switches featuring both axial and tetrahedral chirality. J Mater Chem C, 2013, 1: 7346–7356
Boelke J, Hecht S. Designing molecular photoswitches for soft materials applications. Adv Opt Mater, 2019, 7: 1900404
Probst C, Meichner C, Kreger K, et al. Athermal azobenzene-based nanoimprint lithography. Adv Mater, 2016, 28: 2624–2628
Xue X, Wang H, Han Y, et al. Photoswitchable nonlinear optical properties of metal complexes. Dalton Trans, 2018, 47: 13–22
SAINT: Program for data extraction and reduction. Madison WI: Bruker AXS Inc., 2001
Sheldrick GM. SADABS. Program for empirical adsorption correction of area detector data. Göttingen: University of Gottingen, 2003
Sheldrick GM. Crystal structure refinement with SHELXL. Acta Cryst, 2015, C71: 3–8
Chen S, Zhang W, Wang C, et al. A recycled foam coloring approach based on the reversible photo-isomerization of an azobenzene cationic surfactant. Green Chem, 2016, 18: 3972–3980
Wang H, Bisoyi HK, McConney ME, et al. Visible-light-induced self-organized helical superstructure in orientationally ordered fluids. Adv Mater, 2019, 31: 1902958
Cai Y, Gao Y, Luo Q, et al. Ferrocene-grafted photochromic triads based on a sterically hindered ethene bridge: redox-switchable fluorescence and gated photochromism. Adv Opt Mater, 2016, 4: 1410–1416
He Y, Li Y, Su H, et al. An o-phthalimide-based multistimuli-responsive aggregation-induced emission (AIE) system. Mater Chem Front, 2019, 3: 50–56
McQuade DT, O’Brien AG, Dörr M, et al. Continuous synthesis of pyridocarbazoles and initial photophysical and bioprobe characterization. Chem Sci, 2013, 4: 4067
Villar-Acevedo G, Lugo-Mas P, Blakely MN, et al. Metal-assisted oxo atom addition to an Fe(III) thiolate. J Am Chem Soc, 2017, 139: 119–129
Xu W, Shao Z, Han Y, et al. Light-adjustable third-order nonlinear absorption properties based on a series of hydrazone compounds. Dyes Pigments, 2018, 152: 171–179
Zheng X, Feng M, Li Z, et al. Enhanced nonlinear optical properties of nonzero-bandgap graphene materials in glass matrices. J Mater Chem C, 2014, 2: 4121–4125
Fang Y, Xiao Z, Wu X, et al. Optical nonlinearities and ultrafast all-optical switching of m-plane GaN in the near-infrared. Appl Phys Lett, 2015, 106: 251903
Klotz IM, Fiess HA, Chen Ho JY, et al. The position of the proton in substituted azobenzene molecules. J Am Chem Soc, 1954, 76: 5136–5140
Lovrien R, Pesheck P, Tisel W. Protein and hydrogen ion control of photochromism in aminoazobenzene compounds. J Am Chem Soc, 1974, 96: 244–248
Nihei M, Kurihara M, Mizutani J, et al. Synthesis of azo-conjugated metalladithiolenes and their photo- and proton-responsive isomerization reactions. J Am Chem Soc, 2003, 125: 2964–2973
Wettermark G, Langmuir ME, Anderson DG. Catalysis of the cis → trans isomerization of 2-hydroxy-5-methylazobenzene. J Am Chem Soc, 1965, 87: 476–481
Zhai Y, Xu W, Meng X, et al. Adjusting the third-order nonlinear optical switch performance based on azobenzene derivatives. Acta Chim Sin, 2020, 78: 256–262
Ma CR, Xiao J, Yang GW. Giant nonlinear optical responses of carbyne. J Mater Chem C, 2016, 4: 4692–4698
Sreekumar G, Louie Frobel PG, Sreeja S, et al. Nonlinear absorption and photoluminescence emission in nanocomposite films of fuchsine basic dye-polymer system. Chem Phys Lett, 2011, 506: 61–65
Li L, Shang X, Wang S, et al. Bilayered hybrid perovskite ferroelectric with giant two-photon absorption. J Am Chem Soc, 2018, 140: 6806–6809
Russier-Antoine I, Bertorelle F, Calin N, et al. Ligand-core NLO-phores: A combined experimental and theoretical approach to the two-photon absorption and two-photon excited emission properties of small-ligated silver nanoclusters. Nanoscale, 2017, 9: 1221–1228
Drori J, Rosenberg Y, Bermudez D, et al. Observation of stimulated hawking radiation in an optical analogue. Phys Rev Lett, 2019, 122: 010404
Margulis VA, Muryumin EE, Gaiduk EA. Optical Kerr effect and two-photon absorption in monolayer black phosphorus. J Opt, 2018, 20: 055503
Peruch S, Neira A, Wurtz GA, et al. Geometry defines ultrafast hot-carrier dynamics and Kerr nonlinearity in plasmonic metamaterial waveguides and cavities. Adv Opt Mater, 2017, 5: 1700299
Meng X, Zhou Y, Chen K, et al. Anisotropic saturable and excited-state absorption in bulk ReS2. Adv Opt Mater, 2018, 6: 1800137
Xie Q, Shao Z, Zhao Y, et al. Novel photo-controllable third-order nonlinear optical (NLO) switches based on azobenzene derivatives. Dyes Pigments, 2019, 170: 107599
Jia J, Wu X, Fang Y, et al. Ultrafast broad-band optical limiting in simple hydrazone derivatives with a Π-conjugated system: Effect of two-photon-induced singlet-state absorption. J Phys Chem C, 2018, 122: 16234–16241
Xu W, Wang W, Li J, et al. Two-photon absorption property and excellent optical limiting response of three Schiff base derivatives with large conjugated system. Dyes Pigments, 2019, 160: 1–8
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21671174 and U1904172), the Zhongyuan Thousand Talents Project, the Natural Science Foundation of Henan Province (182300410008), and the Open Foundation of Guangxi Key Laboratory of Processing for Nonferrous Metals and Featured Materials, Guangxi University (2019GXYSOF12).
Author information
Authors and Affiliations
Contributions
Author contributions Xing C and Liu J carried out the experiments and analyzed the date; Hou H conceived the idea; Li K contributed to the improvement of the manuscript; Yang L and Song Y provided technical support; Shao Z, Xu W and Zhao Y contributed to the general discussion. The final version of the manuscript was approved by all authors.
Corresponding authors
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Chang Xing is studying for a master’s degree under the supervision of Prof. Hongwei Hou in Zhengzhou University. Her research interest focuses on the synthesis and application of metal complex with third-order nonlinear optical property.
Kai Li obtained his PhD degree from Tsinghua University in 2014. Now, he is an associate professor at the Department of Chemistry in Zhengzhou University. His research interests mainly focus on the development and application of aggregation-induced emission materials and photo-responsive fluorescent materials.
Hongwei Hou received his PhD degree from Nanjing University in 1995. He works as a professor at the Department of Chemistry in Zhengzhou University since he returned from Singapore in 1998. His research interests include the syntheses and applications of nonlinear optical materials and crystalline metal-organic framework (MOF) molecular reactors.
Rights and permissions
About this article
Cite this article
Xing, C., Liu, J., Yang, L. et al. Third-order nonlinear optical adjusting behavior in azobenzene metal complexes. Sci. China Mater. 64, 408–419 (2021). https://doi.org/10.1007/s40843-020-1429-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-020-1429-9