Supramolecular Metal Halide Complexes for High-Temperature Nonlinear Optical Switches

Wang, Qian; Jin, Jianbo; Wang, Zhongxuan; Ren, Shenqiang; Ye, Qingyu; Dou, Yixuan; Liu, Sunhao; Morris, Amanda; Slebodnick, Carla; Quan, Lina

doi:10.1021/jacs.3c13079

Title: Supramolecular Metal Halide Complexes for High-Temperature Nonlinear Optical Switches

Journal Article · 22 February 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c13079 · OSTI ID:2337766

Wang, Qian ^[1];

^[2]; Wang, Zhongxuan ^[3];

^[3]; Ye, Qingyu ^[4];

^[4]; Liu, Sunhao ^[4];

^[4];

^[4]

Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States); University of Maryland
University of California, Berkeley, CA (United States)
University of Maryland, College Park, MD (United States)
Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States)

Nonlinear optical (NLO) switching materials, which exhibit reversible intensity modulation in response to thermal stimuli, have found extensive applications across diverse fields, including sensing, photoelectronics, and photonic applications. While significant progress has been made in solid-state NLO switching materials, these materials typically showcase their highest NLO performance near room temperature. However, this performance drastically deteriorates upon heating, primarily due to the phase transition undergone by the materials from non-centrosymmetric to centrosymmetric phase. Here, we introduce a new class of NLO switching materials, solid-state supramolecular compounds 18-Crown-6 ether@Cu₂Cl₄·4H₂O (1·4H₂O), exhibiting reversible and stable NLO switching when subjected to near-infrared (NIR) photoexcitation and/or thermal stimuli. The reversible crystal structure in response to external stimuli is attributed to the presence of a weakly coordinated bridging water molecule, facilitated by hydrogen bonding/chelation interactions between the metal halide and crown-ether supramolecules. We observed an exceptionally high second-harmonic generation (SHG) signal under continuous photoexcitation, even at temperatures exceeding 110°C. In addition, the bridging water molecules within the complex can be released and recaptured in a fully reversible manner, all without requiring excessive energy input. This feature allows for precise control of SHG signal activation and deactivation through structural transformations, resulting in a high-contrast off/on ratio, reaching values in the million-fold range.

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Research Organization:: University of Maryland, College Park, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0018631

OSTI ID:: 2337766

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 13 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (48)

Efficient, Reversible Redox-Switching of Molecular First Hyperpolarizabilities in Ruthenium(II) Complexes Possessing Large Quadratic Optical Nonlinearities Coe, Benjamin J.; Houbrechts, Stephan; Asselberghs, Inge Angewandte Chemie International Edition, Vol. 38, Issue 3 https://doi.org/10.1002/(SICI)1521-3773(19990201)38:3<366::AID-ANIE366>3.0.CO;2-D	journal	February 1999
The First Improper Ferroelectric of 2D Multilayered Hybrid Perovskite Enabling Strong Tunable Polarization‐Directed Second Harmonic Generation Effect Ma, Yu; Wang, Jiaqi; Guo, Wuqian Advanced Functional Materials, Vol. 31, Issue 37 https://doi.org/10.1002/adfm.202103012	journal	June 2021
Molecular Dynamics of Flexible Polar Cations in a Variable Confined Space: Toward Exceptional Two-Step Nonlinear Optical Switches Xu, Wei-Jian; He, Chun-Ting; Ji, Cheng-Min Advanced Materials, Vol. 28, Issue 28 https://doi.org/10.1002/adma.201600895	journal	May 2016
Light Emission of Self‐Trapped Excitons in Inorganic Metal Halides for Optoelectronic Applications Guo, Qingxun; Zhao, Xue; Song, Boxiang Advanced Materials, Vol. 34, Issue 52 https://doi.org/10.1002/adma.202201008	journal	June 2022
The Discovery of Crown Ethers (Noble Lecture) Pedersen, Charles J. Angewandte Chemie International Edition in English, Vol. 27, Issue 8 https://doi.org/10.1002/anie.198810211	journal	August 1988
Efficient Photoswitching of the Nonlinear Optical Properties of Dipolar Photochromic Zinc(II) Complexes Aubert, Vincent; Guerchais, Véronique; Ishow, Eléna Angewandte Chemie International Edition, Vol. 47, Issue 3 https://doi.org/10.1002/anie.200704138	journal	December 2007
Electron‐Transfer Photochromism To Switch Bulk Second‐Order Nonlinear Optical Properties with High Contrast Li, Pei‐Xin; Wang, Ming‐Sheng; Zhang, Ming‐Jian Angewandte Chemie International Edition, Vol. 53, Issue 43 https://doi.org/10.1002/anie.201406554	journal	September 2014
An Exceptional Thermally Induced Four‐State Nonlinear Optical Switch Arising from Stepwise Molecular Dynamic Changes in a New Hybrid Salt Zeng, Ying; Hu, Chun‐Li; Xu, Wei‐Jian Angewandte Chemie International Edition, Vol. 61, Issue 2 https://doi.org/10.1002/anie.202110082	journal	November 2021
Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H₂O Vapor Sorption Azmy, Ali; Li, Shunran; Angeli, Giasemi K. Angewandte Chemie International Edition, Vol. 62, Issue 12 https://doi.org/10.1002/anie.202218429	journal	February 2023
Multi‐Stimuli Responsive Luminescence and Domino Phase Transition of Hybrid Copper Halides with Nonlinear Optical Switching Behavior Wu, Jiajing; Guo, Yue; Qi, Jing‐Li Angewandte Chemie International Edition, Vol. 62, Issue 18 https://doi.org/10.1002/anie.202301937	journal	March 2023
The crystal structure of a heterobimetallic crown ether complex: [Na(dibenzo-18-crown-6)][FeCl4] Rogers, Robin D.; Song, Ying Journal of Chemical Crystallography, Vol. 25, Issue 9 https://doi.org/10.1007/BF01667027	journal	September 1995
Aerobic oxidation of alkanes in the presence of acetaldehyde catalysed by copper-crown ether Komiya, Naruyoshi; Naota, Takeshi; Murahashi, Shun-Ichi Tetrahedron Letters, Vol. 37, Issue 10 https://doi.org/10.1016/0040-4039(96)00074-3	journal	March 1996
Wave-Equation Description of Nonlinear Optical Interactions Boyd, Robert W. Nonlinear Optics https://doi.org/10.1016/B978-0-12-369470-6.00002-2	book	January 2008
First- and second-sphere coordination chemistry of alkali metal crown ether complexes Steed, Jonathan W. Coordination Chemistry Reviews, Vol. 215, Issue 1 https://doi.org/10.1016/S0010-8545(01)00317-4	journal	May 2001
Resonant Nonlinear Optics in Phase-Coherent Media Lukin, M. D.; Hemmer, P. R.; Scully, M. O. Advances In Atomic, Molecular, and Optical Physics https://doi.org/10.1016/S1049-250X(08)60190-1	book	January 2000
Supramolecular Approach for Fine-Tuning of the Bright Luminescence from Zero-Dimensional Antimony(III) Halides Morad, Viktoriia; Yakunin, Sergii; Kovalenko, Maksym V. ACS Materials Letters, Vol. 2, Issue 7 https://doi.org/10.1021/acsmaterialslett.0c00174	journal	June 2020
Highly Enhanced Third-Harmonic Generation in 2D Perovskites at Excitonic Resonances Abdelwahab, Ibrahim; Grinblat, Gustavo; Leng, Kai ACS Nano, Vol. 12, Issue 1 https://doi.org/10.1021/acsnano.7b07698	journal	December 2017
Design, Synthesis, Structural and Nonlinear Optical Properties of Photochromic Crystals: Toward Reversible Molecular Switches Sliwa, Michel; Létard, Sylvie; Malfant, Isabelle Chemistry of Materials, Vol. 17, Issue 18 https://doi.org/10.1021/cm050929o	journal	August 2005
Nonlinear Optical Switching Behavior in the Solid State: A Theoretical Investigation on Anils Ségerie, Audrey; Castet, Frédéric; Kanoun, Mohamed Benali Chemistry of Materials, Vol. 23, Issue 17 https://doi.org/10.1021/cm2015516	journal	August 2011
Metal- vs Hydrogen-Bonding Complexation in Zinc Complexes of 18-Crown-6 Doxsee, Kenneth M.; Hagadorn, John R.; Weakley, Timothy J. R. Inorganic Chemistry, Vol. 33, Issue 12 https://doi.org/10.1021/ic00090a020	journal	June 1994
Inclusion of a Cu²⁺ Ion by a Large-Cavity Crown Ether Dibenzo-24-Crown-8 through Supramolecular Interactions Shivaiah, Vaddypally; Das, Samar K. Inorganic Chemistry, Vol. 44, Issue 21 https://doi.org/10.1021/ic051176a	journal	September 2005
Cyclic polyethers and their complexes with metal salts Pedersen, Charles J. Journal of the American Chemical Society, Vol. 89, Issue 26 https://doi.org/10.1021/ja01002a035	journal	December 1967
NH ₂ -MIL-53(Al): A High-Contrast Reversible Solid-State Nonlinear Optical Switch Serra-Crespo, Pablo; van der Veen, Monique A.; Gobechiya, Elena Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja300655f	journal	May 2012
Solid State Molecular Dynamic Investigation of An Inclusion Ferroelectric: [(2,6-Diisopropylanilinium)([18]crown-6)]BF ₄ Ye, Heng-Yun; Li, Shen-Hui; Zhang, Yi Journal of the American Chemical Society, Vol. 136, Issue 28 https://doi.org/10.1021/ja503344b	journal	June 2014
Observation of Vortex Domains in a Two-Dimensional Lead Iodide Perovskite Ferroelectric Zhang, Han-Yue; Song, Xian-Jiang; Chen, Xiao-Gang Journal of the American Chemical Society, Vol. 142, Issue 10 https://doi.org/10.1021/jacs.0c00371	journal	February 2020
Solid-State Nonlinear Optical Switch with the Widest Switching Temperature Range Owing to Its Continuously Tunable T_c Pan, Chun-Ya; Yang, Xin-Rui; Xiong, Lin Journal of the American Chemical Society, Vol. 142, Issue 13 https://doi.org/10.1021/jacs.0c01741	journal	March 2020
18-Crown-6 Coordinated Metal Halides with Bright Luminescence and Nonlinear Optical Effects Merzlyakova, Elena; Wolf, Silke; Lebedkin, Sergei Journal of the American Chemical Society, Vol. 143, Issue 2 https://doi.org/10.1021/jacs.0c09454	journal	January 2021
Strong Second- and Third-Harmonic Generation in 1D Chiral Hybrid Bismuth Halides Yao, Li; Zeng, Zhouxiaosong; Cai, Chengkun Journal of the American Chemical Society, Vol. 143, Issue 39 https://doi.org/10.1021/jacs.1c06567	journal	September 2021
Supramolecular Assembly of Halide Perovskite Building Blocks Zhu, Cheng; Jin, Jianbo; Gao, Mengyu Journal of the American Chemical Society, Vol. 144, Issue 27 https://doi.org/10.1021/jacs.2c04357	journal	June 2022
Unusual High-Temperature Reversible Phase-Transition Behavior, Structures, and Dielectric–Ferroelectric Properties of Two New Crown Ether Clathrates Tang, Yun-Zhi; Yu, Yin-Mei; Xiong, Jian-Bo Journal of the American Chemical Society, Vol. 137, Issue 41 https://doi.org/10.1021/jacs.5b08061	journal	October 2015
Plastic Transition to Switch Nonlinear Optical Properties Showing the Record High Contrast in a Single-Component Molecular Crystal Sun, Zhihua; Chen, Tianliang; Liu, Xitao Journal of the American Chemical Society, Vol. 137, Issue 50 https://doi.org/10.1021/jacs.5b11088	journal	December 2015
Two-Dimensional Organic–Inorganic Perovskite Ferroelectric Semiconductors with Fluorinated Aromatic Spacers Shi, Ping-Ping; Lu, Si-Qi; Song, Xian-Jiang Journal of the American Chemical Society, Vol. 141, Issue 45 https://doi.org/10.1021/jacs.9b10048	journal	October 2019
Room-temperature ferroelectricity in CuInP2S6 ultrathin flakes Liu, Fucai; You, Lu; Seyler, Kyle L. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12357	journal	August 2016
Ferroelectricity and polarity control in solid-state flip-flop supramolecular rotators Akutagawa, Tomoyuki; Koshinaka, Hiroyuki; Sato, Daisuke Nature Materials, Vol. 8, Issue 4 https://doi.org/10.1038/nmat2377	journal	February 2009
Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals Frohna, Kyle; Deshpande, Tejas; Harter, John Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04212-w	journal	May 2018
Direct observation of geometric and sliding ferroelectricity in an amphidynamic crystal Miao, Le-Ping; Ding, Ning; Wang, Na Nature Materials, Vol. 21, Issue 10 https://doi.org/10.1038/s41563-022-01322-1	journal	August 2022
Direct evidence of correlation between the second harmonic generation anisotropy patterns and the polarization orientation of perovskite ferroelectric Wang, Jie-su; Jin, Kui-juan; Gu, Jun-xing Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-09339-2	journal	August 2017
MnBr₂/18-crown-6 coordination complexes showing high room temperature luminescence and quantum yield Hausmann, David; Kuzmanoski, Ana; Feldmann, Claus Dalton Transactions, Vol. 45, Issue 15 https://doi.org/10.1039/C6DT00458J	journal	January 2016
A novel acid-controlled second-order nonlinear optical switch based on dimethyldihydropyrene/cyclophanediene photoswitch Yao, Yao; Xu, Hong-Liang; Su, Zhong-Min Journal of Materials Chemistry C, Vol. 10, Issue 34 https://doi.org/10.1039/D2TC02521C	journal	January 2022
Synthetic and structural studies of tin(IV) complexes of crown ethers Cusack, Paul A.; Patel, Bhagwati N.; Smith, Peter J. Journal of the Chemical Society, Dalton Transactions, Issue 6 https://doi.org/10.1039/DT9840001239	journal	January 1984
Nonlinear optical properties of halide perovskites and their applications Zhou, Yixuan; Huang, Yuanyuan; Xu, Xinlong Applied Physics Reviews, Vol. 7, Issue 4 https://doi.org/10.1063/5.0025400	journal	December 2020
Hydrogen-bonded Networks in Crown Ether Complexes of Hydrated Metal Ions Junk, Peter C.; Lynch, Susan M.; McCool, Brian J. Supramolecular Chemistry, Vol. 9, Issue 2 https://doi.org/10.1080/10610279808034980	journal	May 1998
4-Methoxyanilinium Perrhenate 18-Crown-6: A New Ferroelectric with Order Originating in Swinglike Motion Slowing Down Fu, Da-Wei; Cai, Hong-Ling; Li, Shen-Hui Physical Review Letters, Vol. 110, Issue 25 https://doi.org/10.1103/PhysRevLett.110.257601	journal	June 2013
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Metal-free ferroelectric halide perovskite exhibits visible photoluminescence correlated with local ferroelectricity Handa, Taketo; Hashimoto, Ruito; Yumoto, Go Science Advances, Vol. 8, Issue 25 https://doi.org/10.1126/sciadv.abo1621	journal	June 2022
Cryptands and Cryptates Fabbrizzi, Luigi https://doi.org/10.1142/q0107	book	January 2018

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Title: Supramolecular Metal Halide Complexes for High-Temperature Nonlinear Optical Switches

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