Periodic Reporting for period 1 - AniMOC (Directional Assembly of Emergent Luminescent and Anisotropic d10 Coinage Metal Organic Chalcogenolate Nanomaterials for Fabrication of Pressure Sensitive Devices)
Periodo di rendicontazione: 2021-09-01 al 2022-08-31
Touch is a sense that still remains difficult to mimic, as it requires the development of pressure sensors with high spatial resolution, high sensitivity and fast response time. To date, pressure sensitive devices utilise capacitive, piezo- or tribo-electric mechanisms, which do not allow direct visualisation of the touch/pressure. For spontaneous visual reading, light, associated to its palette of colors, is probably the best response to the variation of applied pressures. New light-emissive devices responsive upon touch or pressure will support growth for smart technologies such as e-skin, interactive clothing, robotics, touchpad screens, medical monitoring devices…etc. Today, there is thus a tremendous need of new optoelectronic devices for spontaneous and visual reading of the pressure through high-spatial resolution.
The strategy of AniMOC project, to generate highly pressure sensitive materials, is to use luminescent and anisotropic nanomaterials, in order to apply a directional strain on the targeted bonds involved in the optoelectronic processes. In order to avoid platinum, iridium and lanthanide-based molecular compounds, that are considered as Critical Raw Materials (CRM) by the European Union, d10 coinage metals (Cu, Ag and Au) represent a good alternative, for their sustainability, affordability and their photoluminescence properties. More importantly, d10 coinage metals compounds can exhibit luminescence mechanochromism under soft pressure associated to a shift of the emission inducing different colours. This reversible pressure effect is due to the presence of weak metallophilic interactions that are involved in the luminescent mechanism and that are highly sensitive to structural changes upon mechanical strain. In this project a new family of highly stable, dense and anisotropic luminescent d10 coinage metal bridged by thiolate ligands, that are named Metal Organic Chalcogenolates (MOCs) coordination polymers (CPs). Thus, the objectives were (i) to obtain nanowires and nanosheets of the anisotropic MOCs, (ii) to control their external functionalization, (iii) to couple and organize them to generate aligned nanowires and packed nanosheets and (iv) to build strain sensitive emissive thin films with orientated MOCs. This project allows to discover three new families of MOC nanomaterials having different dimensionalities, different external functionalities, phase change abilities, and two methods of film formations were tested to get luminescent sensors.
The strategy of AniMOC project, to generate highly pressure sensitive materials, is to use luminescent and anisotropic nanomaterials, in order to apply a directional strain on the targeted bonds involved in the optoelectronic processes. In order to avoid platinum, iridium and lanthanide-based molecular compounds, that are considered as Critical Raw Materials (CRM) by the European Union, d10 coinage metals (Cu, Ag and Au) represent a good alternative, for their sustainability, affordability and their photoluminescence properties. More importantly, d10 coinage metals compounds can exhibit luminescence mechanochromism under soft pressure associated to a shift of the emission inducing different colours. This reversible pressure effect is due to the presence of weak metallophilic interactions that are involved in the luminescent mechanism and that are highly sensitive to structural changes upon mechanical strain. In this project a new family of highly stable, dense and anisotropic luminescent d10 coinage metal bridged by thiolate ligands, that are named Metal Organic Chalcogenolates (MOCs) coordination polymers (CPs). Thus, the objectives were (i) to obtain nanowires and nanosheets of the anisotropic MOCs, (ii) to control their external functionalization, (iii) to couple and organize them to generate aligned nanowires and packed nanosheets and (iv) to build strain sensitive emissive thin films with orientated MOCs. This project allows to discover three new families of MOC nanomaterials having different dimensionalities, different external functionalities, phase change abilities, and two methods of film formations were tested to get luminescent sensors.
The work performed in this project has been done on three new families of MOC nanomaterials: two 1D CPs, [M(o-SPhCO2H/Me)]n M = Cu, Ag, Au and a gold phenylethanethiolate, [Au(SEtPh)]n, that exhibits two successive phase changes upon heat, and a 3D network, [Ag2(1,3-BDT)]n (BDT = benzenedithiolate). Composite films of the yellow emissive [Ag(o-SPhCO2Me)]n mixed with the blue emissive coumarin nanoparticles in an organic matrix, the PVDF (polyvinylidenefluoride) lead to dual emission that is depend with the temperature, up to 120 ˚C, offering great potential for optical thermometry. The formation of transparent and non-luminescent glass of pure amorphous [Au(SEtPh)]n system allows to heat induced local phase changes that are still transparent, but show red emission giving new opportunities for temperature and pressure sensing glasses. Finally the 3D [Ag2(1,3-BDT)]n network, that is a chiral structure, exhibits unprecedented optical properties mixing non linear response and up-conversion. This work has been partially published in three papers:
(1) S. Hawila, A. Abdallah, J.-L. Rukemampunzi, A. Fateeva, G. Ledoux, R. Debord, S. Paihlès, N. Guillou, F. Massuyeau, R. Gautier, A. Mesbah, A Demessence. Chem. Commun., 2022, 58, 8081. A Chiral 3D Silver(I)-Benzenedithiolate Coordination Polymer exhibiting Photoemission and Non-Linear Optical Response. (Invitation in ChemComm Pioneering Investigators collection)
(2) O. Veselska, S. Vaidya, C. Das, N. Guillou, P. Bordet, A. Fateeva, F. Toche, R. Chiriac, G. Ledoux, S. Wuttke, S. Horike, A. Demessence. Angew. Chem. Int. Ed. 2022, 61, e202117261. Cyclic solid-state multiple phase changes with tuned photoemission in a gold thiolate coordination polymer. (HOT PAPER).
(3) O. Veselska, N. Guillou, M. Diaz-Lopez, P. Bordet, G. Ledoux, S. Lebègue, A. Mesbah, A. Fateeva, A. Demessence, ChemPhotoChem, 2022, 6, e202200030. Sustainable and efficient low-energy light emitters: a series of one-dimensional d10 coinage Metal Organic Chalcogenolates, [M(o-SPhCO2H)]n.
(1) S. Hawila, A. Abdallah, J.-L. Rukemampunzi, A. Fateeva, G. Ledoux, R. Debord, S. Paihlès, N. Guillou, F. Massuyeau, R. Gautier, A. Mesbah, A Demessence. Chem. Commun., 2022, 58, 8081. A Chiral 3D Silver(I)-Benzenedithiolate Coordination Polymer exhibiting Photoemission and Non-Linear Optical Response. (Invitation in ChemComm Pioneering Investigators collection)
(2) O. Veselska, S. Vaidya, C. Das, N. Guillou, P. Bordet, A. Fateeva, F. Toche, R. Chiriac, G. Ledoux, S. Wuttke, S. Horike, A. Demessence. Angew. Chem. Int. Ed. 2022, 61, e202117261. Cyclic solid-state multiple phase changes with tuned photoemission in a gold thiolate coordination polymer. (HOT PAPER).
(3) O. Veselska, N. Guillou, M. Diaz-Lopez, P. Bordet, G. Ledoux, S. Lebègue, A. Mesbah, A. Fateeva, A. Demessence, ChemPhotoChem, 2022, 6, e202200030. Sustainable and efficient low-energy light emitters: a series of one-dimensional d10 coinage Metal Organic Chalcogenolates, [M(o-SPhCO2H)]n.
This project confirms the great potential of d10 Metal Organic Thiolate Coordination polymers as multifunctional and sustainable materials. The discoveries done in this project show that these luminescent and hybrid compounds can be used for temperature reading, allowing intrinsic thermometry in systems. More importantly, the gold-thiolate phase change material is the first example of a coordination polymer exhibiting in the solid state two successive crystallisation at temperature below 200 ˚C from the amorphous phase, with each phase associated to different photoluminescent intensities. This reversible phase change material (PCM) represents great opportunities to replace the actual inorganic and toxic PCM that are used in memories using PC-RAM (Phase Change Random Access Memories) technology, allowing to use lower temperatures to save energy, and having flexibility for easy device fabrication and better local phase change control.