Optical Waveguiding Charge-Transfer Cocrystals: Examining the Impact of Molecular Rotations on Their Photoluminescence

Navarro-Huerta, Armando; Matsuo, Takumi; Mikherdov, Alexander S.; Blahut, Jan; Bartůňková, Erika; Jiang, Pingyu; Dračínský, Martin; Teat, Simon; Jin, Mingoo; Hayashi, Shotaro; Rodríguez-Molina, Braulio

doi:10.1021/jacs.4c15957

Optical Waveguiding Charge-Transfer Cocrystals: Examining the Impact of Molecular Rotations on Their Photoluminescence

Journal Article · Wed Feb 26 00:00:00 UTC 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c15957· OSTI ID:2562654

^[1]; ^[2]; ^[3]; ^[4]; Bartůňková, Erika ^[4]; Jiang, Pingyu ^[3]; Dračínský, Martin ^[4]; Teat, Simon ^[5]; ^[3]; ^[2]; ^[1]

Universidad Nacional Autonoma de Mexico (UNAM), Mexico City (Mexico)
Kochi University of Technology, Kami City, Kochi (Japan)
Hokkaido University, Sapporo (Japan)
Czech Academy of Sciences (CAS), Prague (Czech Republic)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Here, we present the first example of a binary optical waveguiding (OWG) cocrystal with large anisotropy featuring a fluorinated acceptor molecule (CPP-TFPN, 1) with on-plane rotational dynamics, confirmed by solid-state NMR (¹⁹F T₁) and theoretical calculations. Spatially resolved microphotoluminescence and variable-temperature photoluminescence experiments allowed us to examine the OWG performance and photophysical properties of both single crystals and bulk microcrystalline samples. A comparison with an analogous cocrystal containing a regioisomeric acceptor (CPP-TFTN, 2) revealed that the photoluminescence characteristics of 1 are associated with the rotational motions of the acceptor, offering insights into how the molecular motion changes this property.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2562654

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 10 Vol. 147; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (45)

Crafting Near‐Infrared Photonics via the Programmable Assembly of Organic Heterostructures at Multiscale Level Xia, Xing‐Yu; Lv, Qiang; Xu, Chao‐Fei Advanced Functional Materials, Vol. 34, Issue 24 https://doi.org/10.1002/adfm.202312478	journal	February 2024
Cocrystal Engineering: A Collaborative Strategy toward Functional Materials Sun, Lingjie; Wang, Yu; Yang, Fangxu Advanced Materials, Vol. 31, Issue 39 https://doi.org/10.1002/adma.201902328	journal	July 2019
Morphology‐Dependent Luminescence and Optical Waveguide Property in Large‐Size Organic Charge Transfer Cocrystals with Anisotropic Spatial Distribution of Transition Dipole Moment Wang, Jing; Zhang, Shitong; Xu, Shuping Advanced Optical Materials, Vol. 8, Issue 2 https://doi.org/10.1002/adom.201901280	journal	November 2019
Recent Advances on Molecular Crystalline Luminescent Materials for Optical Waveguides Wu, Siqin; Zhou, Bo; Yan, Dongpeng Advanced Optical Materials, Vol. 9, Issue 23 https://doi.org/10.1002/adom.202001768	journal	January 2021
Unique 2D Face Topologies in Naphthyl‐Appended Naphtho[k]fluoranthene‐Based 3D Crystals for Optical Waveguide Hino, Yuto; Matsuo, Takumi; Hayashi, Shotaro Advanced Optical Materials, Vol. 11, Issue 13 https://doi.org/10.1002/adom.202201810	journal	February 2023
Controlling Morphological Dimensions of Organic Charge‐Transfer Cocrystal by Manipulating the Growth Kinetics for Optical Waveguide Applications Wu, Bin; Zhuo, Ming‐Peng; Chen, Song Advanced Optical Materials, Vol. 11, Issue 12 https://doi.org/10.1002/adom.202202895	journal	March 2023
One‐dimensional molecular co‐crystal alloys capable of full‐color emission for low‐loss optical waveguide and optical logic gate Qi, Zhenhong; Ma, Yu‐Juan; Yan, Dongpeng Aggregate, Vol. 5, Issue 1 https://doi.org/10.1002/agt2.411	journal	August 2023
Controlling the Structures and Photonic Properties of Organic Nanomaterials by Molecular Design Yao, Wei; Yan, Yongli; Xue, Lin Angewandte Chemie International Edition, Vol. 52, Issue 33 https://doi.org/10.1002/anie.201302894	journal	July 2013
2D Organic Photonics: An Asymmetric Optical Waveguide in Self-Assembled Halogen-Bonded Cocrystals Zhuo, Ming-Peng; Tao, Yi-Chen; Wang, Xue-Dong Angewandte Chemie International Edition, Vol. 57, Issue 35 https://doi.org/10.1002/anie.201806149	journal	August 2018
Orientation‐Controlled 2D Anisotropic and Isotropic Photon Transport in Co‐crystal Polymorph Microplates Liu, Yong; Hu, Huiping; Xu, Ling Angewandte Chemie International Edition, Vol. 59, Issue 11 https://doi.org/10.1002/anie.201913441	journal	January 2020
Manipulating Light‐Induced Dynamic Macro‐Movement and Static Photonic Properties within 1D Isostructural Hydrogen‐Bonded Molecular Cocrystals Li, Shuzhen; Lu, Bo; Fang, Xiaoyu Angewandte Chemie International Edition, Vol. 59, Issue 50 https://doi.org/10.1002/anie.202009714	journal	October 2020
Non‐Covalent Supramolecular 1D Alternating Copolymer in Crystal toward 2D Anisotropic Photon Transport Nakabayashi, Mahiro; Matsuo, Takumi; Hayashi, Shotaro Chemistry – A European Journal, Vol. 29, Issue 61 https://doi.org/10.1002/chem.202302351	journal	September 2023
1D Mixed‐Stack Cocrystals Based on Perylene Diimide toward Ambipolar Charge Transport Yu, Panpan; Li, Yang; Zhao, Huijuan Small, Vol. 17, Issue 20 https://doi.org/10.1002/smll.202006574	journal	April 2021
Organic Cocrystal Alloys: From Three Primary Colors to Continuously Tunable Emission and Applications on Optical Waveguides and Displays Zhang, Jia‐Xuan; Zhao, Shuai; Jiang, Jia‐Hao Small, Vol. 20, Issue 33 https://doi.org/10.1002/smll.202400313	journal	March 2024
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
TCNQ-based organic cocrystal integrated red emission and n-type charge transport Jiang, Mengjia; Li, Shuyu; Zhen, Chun Frontiers of Optoelectronics, Vol. 15, Issue 1 https://doi.org/10.1007/s12200-022-00022-7	journal	May 2022
Selective epitaxial growth of organic heterostructure via cocrystal engineering: Towards oriented signal conversion Lv, Qiang; Wang, Xue-Dong; Yu, Yue Science China Materials, Vol. 66, Issue 10 https://doi.org/10.1007/s40843-023-2561-8	journal	September 2023
Multistimuli-Responsive Fluorescent Switches Based on Reversible Decomposition and Regeneration of charge-transfer Complexes Chen, Qiao; Chen, Xinyu; Han, Yanning Crystal Growth & Design, Vol. 22, Issue 1 https://doi.org/10.1021/acs.cgd.1c01208	journal	November 2021
Multicolor Emission of Organic Microcrystals with Charge Transfer Interactions through Cocrystal Engineering Zhang, He; Lin, Dong-Qing; Wu, Ming-Zai Crystal Growth & Design, Vol. 23, Issue 9 https://doi.org/10.1021/acs.cgd.3c00490	journal	August 2023
Synthesis of a Carbazole-[pi]-carbazole Molecular Rotor with Fast Solid State Intramolecular Dynamics and Crystallization-Induced Emission Aguilar-Granda, Andrés; Pérez-Estrada, Salvador; Roa, Arian E. Crystal Growth & Design, Vol. 16, Issue 6 https://doi.org/10.1021/acs.cgd.6b00395	journal	May 2016
Impact of Hydrogen and Halogen Bonding Interactions on the Packing and Ionicity of Charge-Transfer Cocrystals Goud, N. Rajesh; Matzger, Adam J. Crystal Growth & Design, Vol. 17, Issue 1 https://doi.org/10.1021/acs.cgd.6b01548	journal	December 2016
Crystals of Charge-Transfer Complexes with Reorienting Polar Molecules: Dielectric Properties and Order–Disorder Phase Transitions Harada, Jun; Yoneyama, Naho; Sato, Shota Crystal Growth & Design, Vol. 19, Issue 1 https://doi.org/10.1021/acs.cgd.8b01418	journal	December 2018
Influence of Internal Molecular Motions in the Photothermal Conversion Effect of Charge-Transfer Cocrystals Navarro-Huerta, Armando; Hall, David A.; Blahut, Jan Chemistry of Materials, Vol. 35, Issue 23 https://doi.org/10.1021/acs.chemmater.3c01944	journal	November 2023
Role of Conical Intersections on the Efficiency of Fluorescent Organic Molecular Crystals Rivera, Miguel; Stojanović, Ljiljana; Crespo-Otero, Rachel The Journal of Physical Chemistry A, Vol. 125, Issue 4 https://doi.org/10.1021/acs.jpca.0c11072	journal	January 2021
Unprecedented Improvement of Near-Infrared Photothermal Conversion Efficiency to 87.2% by Ultrafast Non-radiative Decay of Excited States of Self-Assembly Cocrystal Chen, Wenbin; Sun, Shanshan; Huang, Guanheng The Journal of Physical Chemistry Letters, Vol. 12, Issue 24 https://doi.org/10.1021/acs.jpclett.1c01021	journal	June 2021
Optical Waveguide and Photoluminescent Polarization in Organic Cocrystal Polymorphs Du, Sijia; Ma, Suqian; Xu, Bin The Journal of Physical Chemistry Letters, Vol. 12, Issue 38 https://doi.org/10.1021/acs.jpclett.1c02726	journal	September 2021
How Inter- and Intramolecular Processes Dictate Aggregation-Induced Emission in Crystals Undergoing Excited-State Proton Transfer Dommett, Michael; Rivera, Miguel; Crespo-Otero, Rachel The Journal of Physical Chemistry Letters, Vol. 8, Issue 24 https://doi.org/10.1021/acs.jpclett.7b02893	journal	December 2017
Manipulating Interfacial Charge-Transfer Absorption of Cocrystal Absorber for Efficient Solar Seawater Desalination and Water Purification Tian, Shuang; Huang, Zhongming; Tan, Jihua ACS Energy Letters, Vol. 5, Issue 8 https://doi.org/10.1021/acsenergylett.0c01466	journal	July 2020
Epitaxial Growth of Nanorod Meshes from Luminescent Organic Cocrystals via Crystal Transformation Sun, Yanqiu; Lei, Yilong; Hu, Wenping Journal of the American Chemical Society, Vol. 142, Issue 16 https://doi.org/10.1021/jacs.0c00135	journal	April 2020
Oriented Self-Assembly of Hierarchical Branch Organic Crystals for Asymmetric Photonics Ma, Yingxin; Xu, Chao-Fei; Mao, Xin-Rui Journal of the American Chemical Society, Vol. 145, Issue 16 https://doi.org/10.1021/jacs.3c02061	journal	April 2023
Rational Design of Charge-Transfer Interactions in Halogen-Bonded Co-crystals toward Versatile Solid-State Optoelectronics Zhu, Weigang; Zheng, Renhui; Zhen, Yonggang Journal of the American Chemical Society, Vol. 137, Issue 34 https://doi.org/10.1021/jacs.5b05586	journal	August 2015
Phosphorescence Control Mediated by Molecular Rotation and Aurophilic Interactions in Amphidynamic Crystals of 1,4-Bis[tri-( p -fluorophenyl)phosphane-gold(I)-ethynyl]benzene Jin, Mingoo; Chung, Tim S.; Seki, Tomohiro Journal of the American Chemical Society, Vol. 139, Issue 49 https://doi.org/10.1021/jacs.7b11316	journal	November 2017
CF₃ Rotation in 3-(Trifluoromethyl)phenanthrene: Solid State ¹⁹F and ¹H NMR Relaxation and Bloch−Wangsness−Redfield Theory Beckmann, Peter A.; Rosenberg, Jessie; Nordstrom, Kerstin The Journal of Physical Chemistry A, Vol. 110, Issue 11 https://doi.org/10.1021/jp056643o	journal	February 2006
Nonexponential Solid State ¹H and ¹⁹F Spin–Lattice Relaxation, Single-crystal X-ray Diffraction, and Isolated-Molecule and Cluster Electronic Structure Calculations in an Organic Solid: Coupled Methyl Group Rotation and Methoxy Group Libration in 4,4′-Dimethoxyoctafluorobiphenyl Fahey, Donald P.; Dougherty, William G.; Kassel, W. Scott The Journal of Physical Chemistry A, Vol. 116, Issue 48 https://doi.org/10.1021/jp3075892	journal	November 2012
1D versus 2D cocrystals growth via microspacing in-air sublimation Ye, Xin; Liu, Yang; Guo, Qing Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08712-1	journal	February 2019
Lattice-mismatch-free growth of organic heterostructure nanowires from cocrystals to alloys Lv, Qiang; Wang, Xue-Dong; Yu, Yue Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-30870-y	journal	June 2022
Highly efficient color-tunable organic co-crystals unveiling polymorphism, isomerism, delayed fluorescence for optical waveguides and cell-imaging Barman, Debasish; Annadhasan, Mari; Bidkar, Anil Parsram Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-42017-8	journal	October 2023
Lateral epitaxial growth of two-dimensional organic heterostructures Lv, Qiang; Wang, Xue-Dong; Yu, Yue Nature Chemistry, Vol. 16, Issue 2 https://doi.org/10.1038/s41557-023-01364-1	journal	November 2023
Hirshfeld surface analysis Spackman, Mark A.; Jayatilaka, Dylan CrystEngComm, Vol. 11, Issue 1 https://doi.org/10.1039/B818330A	journal	January 2009
Tailoring the structures and photonic properties of low-dimensional organic materials by crystal engineering Li, Qing; Jin, Wang; Chu, Manman Nanoscale, Vol. 10, Issue 10 https://doi.org/10.1039/C7NR08228B	journal	January 2018
Self-assembled organic homostructures with tunable optical waveguides fabricated via “cocrystal engineering” Ma, Ying-Xin; Wei, Guo-Qing; Chen, Song Chemical Communications, Vol. 57, Issue 89 https://doi.org/10.1039/D1CC04675F	journal	January 2021
Excited state mechanisms in crystalline carbazole: the role of aggregation and isomeric defects Hernández, Federico J.; Crespo-Otero, Rachel Journal of Materials Chemistry C, Vol. 9, Issue 35 https://doi.org/10.1039/D1TC02019F	journal	January 2021
Preparation of intrinsically fragile bent crystals Seki, Tomohiro; Kobayashi, Shiori; Ishikawa, Rintaro Chemical Science, Vol. 15, Issue 31 https://doi.org/10.1039/D4SC02918F	journal	January 2024
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
A General Synthetic Approach of Organic Lateral Heterostructures for Optical Signal Converters in All-Color Wavelength Lv, Qiang; Wang, Xue-Dong; Yang, Wan-Ying CCS Chemistry, Vol. 5, Issue 2 https://doi.org/10.31635/ccschem.022.202101640	journal	February 2023

Similar Records

Challenges in Transitioning Cocrystals from Bench to Bedside: Dissociation in Prototype Drug Product Environment

Journal Article · Wed Jun 27 00:00:00 UTC 2018 · Molecular Pharmaceutics · OSTI ID:1467704

Nonlinear photoluminescence of fullerene-doped optical glasses

Journal Article · Fri Jun 01 04:00:00 UTC 2001 · Journal of Applied Physics · OSTI ID:40203797

Ferroelectric Polarization and Second Harmonic Generation in Supramolecular Cocrystals with Two Axes of Charge-Transfer

Journal Article · Thu Jun 29 00:00:00 UTC 2017 · Journal of the American Chemical Society · OSTI ID:1821883

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Optical Waveguiding Charge-Transfer Cocrystals: Examining the Impact of Molecular Rotations on Their Photoluminescence

Citation Formats

References (45)

Similar Records

Related Subjects