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A series of amphiphilic platinum(II) complexes with tridentate N-donor ligands has been synthesized and characterized. Different supramolecular architectures are constructed using the amphiphilic molecules as the building blocks through the formation of Pt···Pt and π-π stacking interactions in aqueous media. The aggregation-deaggregation-aggregation self-assembly behavior together with obvious spectroscopic changes could be fine-tuned by the addition of THF in aqueous media. More interestingly, one of the complexes is found to show fast response and high selectivity toward alcohol and water vapors with good reversibility, leading to drastic color and luminescence changes, and hence unique dual switching behavior, with the water molecules readily displaced by the alcohol vapor. Rapid writing and erasure have been realized via the control of a jet or a stream of alcohol vapor flow. In addition, it has been employed as active materials in the fabrication of small-molecule solution-processable resistive memory devices, exhibiting stable and promising binary memory performance with threshold voltages of ca. 3.4 V, high ON/OFF ratios of up to 10 and long retention times of over 10 s. The vapochromic and vapoluminescent materials are demonstrated to have potential applications in chemosensing, logic gates, VOC monitoring, and memory functions.
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http://dx.doi.org/10.1021/jacs.7b07638 | DOI Listing |
Dalton Trans
February 2025
TerraPower LLC, Bellevue, WA 98008, USA.
This study explores the vapochromic and vapoluminescent behaviors of [Pt(tpy)Cl]PF host molecules (tpy = 2,2':6',2''-terpyridine) under acetonitrile (CHCN) vapor guest, challenging the conventional view that these phenomena arise solely from direct host-guest interactions. Our findings reveal a cooperative mechanism where mechanochromic surface perturbations prime the Pt(II) host for guest incorporation, leading to initial color and luminescence changes prior to significant structural alterations. While the color transition between the yellow [Pt(tpy)Cl]PF form and the red/orange [Pt(tpy)Cl]PF·CHCN form is reversible, repeated vapor cycling induces a loss of crystallinity, as indicated by diffraction peak broadening and emission shifts.
View Article and Find Full Text PDFInorg Chem
August 2022
Materials Chemistry Research Center, Department of Chemistry, Faculty of Science, Khon Kaen University, Muang, Khon Kaen 40002, Thailand.
The use of vapor-responsive chromic materials in sensing applications for the detection of harmful volatile organic chemicals is rapidly expanding. Herein, four new amino-functionalized Cu(I) coordination polymers of [CuI(pyt-NH)] () and () and [CuSCN(pyt-NH)] () and () (where pyt-NH = 2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole) were successfully synthesized. Single-crystal X-ray diffraction analysis reveals that and are iodo-based polymorphs, while and are thiocyanato-based polymorphs.
View Article and Find Full Text PDFInorg Chem
July 2022
Departamento de Química-Centro de Síntesis Química de La Rioja (CISQ), Universidad de La Rioja, 26006 Logroño, Spain.
Here, we describe the neutral cyclometalated butylisocyanide Pt complexes, [Pt(CN)Cl(CNBu)] , the double salts [Pt(CN)(CNBu)][Pt(CN)Cl] , and the cationic complexes [Pt(CN)(CNBu)]ClO [C∧N = difluorophenylpyridine (dfppy, ), 4-(2-pyridyl)benzaldehyde (ppy-CHO, )]. A comparative study of the pseudopolymorphs , , , , , and reveals strong aggregation through Pt···Pt and/or π···π stacking interactions to give a variety of distinctive one-dimensional (1D) infinite chains, which modulate the photoluminescent properties. This intermolecular long-range aggregate formation is the main origin of the photoluminescent behavior of and complexes, which exhibit highly sensitive and reversible responses to multiple external stimuli including different volatile organic compounds (VOCs), solvents, temperatures, and pressures, with distinct color and phosphorescent color switching from green to red.
View Article and Find Full Text PDFSci Rep
October 2019
Department of Chemistry, Faculty of Science, Hokkaido University, North-10 West-8, Kita-ku, Sapporo, Hokkaido, 060-0810, Japan.
A hybrid vapoluminescent system exhibiting fast and repeatable response was constructed using periodic mesoporous organosilica with bipyridine moieties (BPy-PMO) and a Pt(II) complex bearing a potentially luminescent 2-phenylpyridinato (ppy) ligand. An intense red luminescence appeared when the Pt(II)-complex immobilised BPy-PMO was exposed to methanol vapour and disappeared on exposure to pyridine vapour. The ON-OFF vapochromic behaviour occurred repeatedly in a methanol/pyridine/heating cycle.
View Article and Find Full Text PDFJ Am Chem Soc
October 2017
Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, P. R. China.
A series of amphiphilic platinum(II) complexes with tridentate N-donor ligands has been synthesized and characterized. Different supramolecular architectures are constructed using the amphiphilic molecules as the building blocks through the formation of Pt···Pt and π-π stacking interactions in aqueous media. The aggregation-deaggregation-aggregation self-assembly behavior together with obvious spectroscopic changes could be fine-tuned by the addition of THF in aqueous media.
View Article and Find Full Text PDF