Inkjet-Printed Photoluminescent Patterns of Aggregation-Induced-Emission Chromophores on Surface-Anchored Metal-Organic Frameworks.

Organic chromophores that exhibit aggregation-induced emission (AIE) are of interest for applications in displays, lighting, and sensing, because they can maintain efficient emission at high molecular concentrations in the solid state. Such advantages over conventional chromophores could allow thinner conversion layers of AIE chromophores to be realized, with benefits in terms of the efficiency of the optical outcoupling, thermal management, and response times. However, it is difficult to create large-area optical quality thin films of efficiently performing AIE chromophores. Here, we demonstrate that this can be achieved by using a surface-anchored metal-organic framework (SURMOF) thin film coating as a host substrate, into which the tetraphenylethylene (TPE)-based AIE chromophore can be printed. We demonstrate that the SURMOF constrains the AIE-chromophore molecular conformation, affording efficient performance even at low loading densities in the SURMOF. As the loading density of the AIE chromophore in the SURMOF is increased, its absorption and emission spectra are tuned due to increased interaction between AIE molecules, but the high photoluminescent quantum yield (PLQY = 50% for this AIE chromophore) is maintained. Lastly, we demonstrate that patterns of the AIE chromophore with 70 μm feature sizes can be easily created by inkjet printing onto the SURMOF substrate. These results foreshadow novel possibilities for the creation of patterned phosphor thin films utilizing AIE chromophores for display or lighting applications.

[1]  B. Richards,et al.  Enhancing the photoluminescence of surface anchored metal-organic frameworks: mixed linkers and efficient acceptors. , 2018, Physical chemistry chemical physics : PCCP.

[2]  C. Wöll,et al.  Surface-supported metal-organic framework thin films: fabrication methods, applications, and challenges. , 2017, Chemical Society reviews.

[3]  David G Lidzey,et al.  Intermolecular states in organic dye dispersions: excimers vs. aggregates , 2017 .

[4]  B. Richards,et al.  Facile loading of thin-film surface-anchored metal-organic frameworks with Lewis-base guest molecules , 2017 .

[5]  Ben Zhong Tang,et al.  Dramatic Differences in Aggregation-Induced Emission and Supramolecular Polymerizability of Tetraphenylethene-Based Stereoisomers. , 2017, Journal of the American Chemical Society.

[6]  Yan‐Song Zheng,et al.  The Fixed Propeller-Like Conformation of Tetraphenylethylene that Reveals Aggregation-Induced Emission Effect, Chiral Recognition, and Enhanced Chiroptical Property. , 2016, Journal of the American Chemical Society.

[7]  Yuning Hong Aggregation-induced emission—fluorophores and applications , 2016, Methods and applications in fluorescence.

[8]  Yeonkyung Lee,et al.  P‐59: Toward High Resolution Inkjet‐Printed Quantum Dot Light‐Emitting Diodes for Next Generation Display , 2016 .

[9]  C. Corminboeuf,et al.  How does tetraphenylethylene relax from its excited states? , 2016, Physical chemistry chemical physics : PCCP.

[10]  T. Heine,et al.  Highly Emissive Covalent Organic Frameworks. , 2016, Journal of the American Chemical Society.

[11]  C. Wöll,et al.  Formation of oriented and patterned films of metal–organic frameworks by liquid phase epitaxy: A review , 2016 .

[12]  Xiaopeng Li,et al.  A Suite of Tetraphenylethylene-Based Discrete Organoplatinum(II) Metallacycles: Controllable Structure and Stoichiometry, Aggregation-Induced Emission, and Nitroaromatics Sensing. , 2015, Journal of the American Chemical Society.

[13]  N. Jana,et al.  Detection and Monitoring of Amyloid Fibrillation Using a Fluorescence "Switch-On" Probe. , 2015, ACS applied materials & interfaces.

[14]  A. Chatterjee,et al.  Fluorescence Turn-on Chemosensor for the Detection of Dissolved CO2 Based on Ion-Induced Aggregation of Tetraphenylethylene Derivative. , 2015, Analytical chemistry.

[15]  Ryan T. K. Kwok,et al.  Aggregation-Induced Emission: Together We Shine, United We Soar! , 2015, Chemical reviews.

[16]  Zhiyu Wang,et al.  Dye Encapsulated Metal‐Organic Framework for Warm‐White LED with High Color‐Rendering Index , 2015 .

[17]  Timothy R. Cook,et al.  Highly emissive platinum(II) metallacages. , 2015, Nature chemistry.

[18]  T. Emge,et al.  Solution processable MOF yellow phosphor with exceptionally high quantum efficiency. , 2014, Journal of the American Chemical Society.

[19]  Roy N. McDougald,et al.  Rigidifying fluorescent linkers by metal-organic framework formation for fluorescence blue shift and quantum yield enhancement. , 2014, Journal of the American Chemical Society.

[20]  Z. Su,et al.  Efficient and tunable white-light emission of metal–organic frameworks by iridium-complex encapsulation , 2013, Nature Communications.

[21]  M. Dincǎ,et al.  Conformational locking by design: relating strain energy with luminescence and stability in rigid metal-organic frameworks. , 2012, Journal of the American Chemical Society.

[22]  B. Tang,et al.  Tetraphenylethene: a versatile AIE building block for the construction of efficient luminescent materials for organic light-emitting diodes , 2012 .

[23]  O. Shekhah,et al.  Surface-anchored MOF-based photonic antennae. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[24]  R. Griffin,et al.  Phenyl ring dynamics in a tetraphenylethylene-bridged metal-organic framework: implications for the mechanism of aggregation-induced emission. , 2012, Journal of the American Chemical Society.

[25]  M. Dincǎ,et al.  Turn-on fluorescence in tetraphenylethylene-based metal-organic frameworks: an alternative to aggregation-induced emission. , 2011, Journal of the American Chemical Society.

[26]  F. Spano The spectral signatures of Frenkel polarons in H- and J-aggregates. , 2010, Accounts of chemical research.

[27]  V. Bulović,et al.  Synthesis of J-aggregating dibenz[a,j]anthracene-based macrocycles. , 2009, Journal of the American Chemical Society.

[28]  Hoi Sing Kwok,et al.  Aggregation-induced emission , 2006, SPIE Optics + Photonics.

[29]  Richard H. Friend,et al.  An improved experimental determination of external photoluminescence quantum efficiency , 1997 .

[30]  Ifor D. W. Samuel,et al.  Measurement of absolute photoluminescence quantum efficiencies in conjugated polymers , 1995 .