Microcontact Click Printing for Templating Ultrathin Films of Metal−Organic Frameworks

“…Finally, unwanted Cu‐TCNQ SURMOF crystals on PMMA surface were removed upon dissolving the matrix polymer in acetone followed by ultrasonication. So far, patterning techniques such as microcontact printing (μCP), dip‐pen nanolithography (DPN), and irradiation‐promoted exchange reaction (IPER) were used for lateral structuring of SURMOF thin‐films . Normally, these techniques are limited to thiolate‐SAM templates on the Au and Ag substrates only and difficult to apply for SAMs on FTO (or ITO) substrates.…”

Section: Resultsmentioning

confidence: 99%

Highly Hydrophobic and Chemically Rectifiable Surface‐Anchored Metal‐Organic Framework Thin‐Film Devices

Rana

Rajendra

Dhara

et al. 2016

Adv Materials Inter

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(MOFs) in common organic solvents which heavily limits thin-film processing on various support substrates for fabrication of devices. SURMOFs are in principle possible to achieve virtually on any support including flexible plastic and cloth substrates with molecular-level control of the dimensionality as well as functionality. [2] Subsequent loading of guest molecules opens-up an immense opportunity of SURMOFs for applications in storage and separation of gas and liquid, making highly specific sensors, performing unconventional catalysis, and overall, for the development of stimuli responsive electronic and magnetic thin-film devices. [3] As for the electronic applications of metal-organics, the experimental challenges are, in general, i) patterning feasibility as thin-films by employing standard lithographic techniques, ii) controllable thickness and orientation, iii) film homogeneity, iv) reasonable porosity, v) desirable electrical conductivity, vi) tuning electrical conductivity of thin-films by physical and chemical stimuli, and finally, vii) stability of the thin-films at ambient conditions, specifically against moisture and heat. At a glance, SURMOFs appear suitable platforms to overcome all these challenges to a considerable extent except the facts that MOFs are i) intrinsically poor conductors of electricity (due to insulating nature of the organic ligands and an energy mismatch in the overlap between ligand's p orbitals and metal ion's d orbitals); and ii) usually nonhydrophobic and sensitive to moisture. [4] Such important issues bring to the origin of this work: How to fabricate SURMOF thin-film devices hydrophobic as well electrically conductive?In order to achieve reasonably good electrical conductivity, so far, HKUST-1-based (a porous metal-organic coordination polymer comprised of Cu ion and 1,3,5-benzene tricarboxylic acid (BTC) ligand (benzene tricarboxylic acid) SURMOF thinfilm device was infiltrated with organic electrophile guest tetracyanoquinodimethane (TCNQ) and the subsequent redoxreaction between Cu 2+ ions and TCNQ molecules resulted in a significant increase in the conductivity value within the semiconducting span. [5] However, HKUST-1-based SURMOF thin-films are not really hydrophobic. Another disadvantage

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“…7b, 18 Recently, we paid particular attention to LnMOF lms based on the ligand 2,2 0 -biquinoline-4,4 0 -dicarboxylate (bqdc 2À ), as bqdc 2À has an intense absorption band in the near-UV region (about 20 000 M À1 cm À1 ) and has a good antenna effect for Eu 3+ . 20 These preserved pyridyl N sites could interact with other metal ions and lead to luminescence intensity changes of Ln 3+ . 20 These preserved pyridyl N sites could interact with other metal ions and lead to luminescence intensity changes of Ln 3+ .…”

Section: Introductionmentioning

confidence: 99%

A novel highly luminescent LnMOF film: a convenient sensor for Hg2+ detecting

et al. 2013

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A highly luminescent LnMOF {[Eu 2 (bqdc) 3 (H 2 O)(DMF) 3 ]$0.5DMF$H 2 O} n (1, bqdc ¼ 2,2 0 -biquinoline-4,4 0dicarboxylate) was designed and synthesized. It was characterized by single crystal X-ray diffraction, PXRD, TGA, EA and FT-IR. A new strategy for preparing mechanically robust MOF thin films was developed by electrodeposition in combination with subsequent solvothermal synthesis. A portable sensor device prototype consisting of a film of 1 was conveniently fabricated by using this new strategy and this sensor device exhibits a highly selective response to Hg 2+ . Its luminescence quenching can be distinguished clearly with the naked eye when illuminated by a handy UV banknote detector. The diffusion kinetics of Hg 2+ into the LnMOF film is first proposed.

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Microcontact Click Printing for Templating Ultrathin Films of Metal−Organic Frameworks

Cited by 35 publications

References 38 publications

Transparent films of metal-organic frameworks for optical applications

Transparent films of metal-organic frameworks for optical applications

Highly Hydrophobic and Chemically Rectifiable Surface‐Anchored Metal‐Organic Framework Thin‐Film Devices

A novel highly luminescent LnMOF film: a convenient sensor for Hg2+ detecting

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