Luminescent coordination-driven supramolecular assemblies based on pre-organized Cu(I) precursors stabilized by main-group element ligands

• Applicant: Professor Dr. Manfred Scheer
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2020 to 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 446028511

• Final Report Year: 2024

Final Report Abstract

Given the deficit of inexpensive and luminescent materials from compounds containing abundant elements as for instance copper, this ANR-DFG SUPRALUM project targeted the preparation and the study of the multifunctional luminescence properties of a large series of new discrete and polymeric polymetallic Cu(I)-based supramolecular assemblies. These new inexpensive and stable derivatives possess unprecedented architectures that include enhanced solid-state luminescence properties, which establish them as a very appealing source of new multifunctional molecular materials incorporating both lighting and sensor applications. A combination of experimental and computational modeling was conducted to integrate fundamental understanding and potential technological applications from coordination chemistry, supramolecular chemistry, main group element chemistry, photophysics and materials science into this project. To do so, specific synthetic methods and complementary characterization skills of the French and German teams were combined. This includes the innovative use of coordination-driven adaptive supramolecular chemistry applied to flexible and pre-assembled Cu(I) precursors as well as the integration of polytopic ligands (e.g. ligands combining main group elements such as phosphorus and arsenic) including flexible polytopic connector ligands. Moreover, the influence of the Weakly Coordinating Anions (WCAs) as counterions on the creation of supramolecular aggregates as well as their influence on the luminescent properties was extensively studied. This synergy made it possible to introduce luminescence properties specific to the synthesized derivatives. In particular, irreversible transitions – activated by temperature – of the solid-state luminescence properties of novel series of compounds have been obtained, opening the way to new fields of application for these photoactive derivatives based on Cu(I) ions. Extensive photophysical studies as well as state-of-the-art theoretical calculations were carried out to characterize and rationalize the electronic processes underlying the new materials obtained.

Publications

• Linking of CuI Units by Tetrahedral Mo2E2 Complexes (E=P, As). Chemistry – A European Journal, 26(64), 14570-14574.
  Schiller, Jana; Schreiner, Andrea; Seidl, Michael; Balázs, Gábor & Scheer, Manfred
  
• The Potential of the Diarsene Complex [(C5H5)2Mo2(CO)4(μ,η2‐As2)] as a Connector Between Silver Ions. Chemistry – A European Journal, 26(63), 14315-14319.
  Moussa, Mehdi Elsayed; Schiller, Jana; Peresypkina, Eugenia; Seidl, Michael; Balázs, Gábor; Shelyganov, Pavel & Scheer, Manfred
  
• Au-Containing Coordination Polymers Based on Polyphosphorus Ligand Complexes. Inorganic Chemistry, 60(8), 6027-6039.
  Brake, Helena; Peresypkina, Eugenia; Virovets, Alexander V.; Kremer, Werner; Klimas, Christian; Schwarzmaier, Christoph & Scheer, Manfred
  
• Coordination-driven supramolecular syntheses of new homo- and hetero-polymetallic Cu(i) assemblies: solid-state and solution characterization. Inorganic Chemistry Frontiers, 8(22), 4887-4895.
  Khalil, Ali Moustafa; Xu, Chendong; Delmas, Vincent; Calvez, Guillaume; Costuas, Karine; Haouas, Mohamed & Lescop, Christophe
  
• Discrete and polymeric organometallic-organic assemblies based on the diarsene complex [(Cp)2Mo2(CO)4(μ,η2-As2)], AgPF6and N-donor organic molecules. New Journal of Chemistry, 45(4), 1800-1804.
  Moussa, Mehdi Elsayed; Schiller, Jana; Seidl, Michael; Shelyganov, Pavel A. & Scheer, Manfred
  
• Mixed Organometallic–Organic Hybrid Assemblies Based on the Diarsene Complex [Cp2Mo2(CO)4(μ,η2‐As2)], AgI Salts and N‐Donor Organic Molecules. Chemistry – A European Journal, 27(15), 5028-5034.
  Elsayed, Moussa Mehdi; Shelyganov, Pavel A.; Seidl, Michael; Peresypkina, Eugenia; Berg, Nele; Gschwind, Ruth M.; Balázs, Gábor; Schiller, Jana & Scheer, Manfred
  
• Versatile Coordination of AgI and CuI Ions towards cyclo‐As5 Ligands. Chemistry – A European Journal, 27(38), 9742-9747.
  Moussa, Mehdi Elsayed; Fleischmann, Martin; Balázs, Gábor; Virovets, Alexander V.; Peresypkina, Eugenia; Shelyganov, Pavel A.; Seidl, Michael; Reichl, Stephan & Scheer, Manfred
  
• Impact of Intermolecular Non‐Covalent Interactions in a CuI8PdII1 Discrete Assembly: Conformers’ Geometries and Stimuli‐Sensitive Luminescence Properties. Chemistry – A European Journal, 28(24).
  Moutier, Florent; Schiller, Jana; Lecourt, Constance; Khalil, Ali Moustafa; Delmas, Vincent; Calvez, Guillaume; Costuas, Karine & Lescop, Christophe
  
• Die Diantimonkomplexe [CpR2Mo2(CO)4(μ,η2‐Sb2)] (CpR=C5H5, C5H4tBu) als unerwartete stabilisierende Liganden von Silber(I)n (n=1–4)‐Monomeren, ‐Dimeren und ‐Ketten. Angewandte Chemie, 135(7).
  Shelyganov, Pavel A.; Elsayed, Moussa Mehdi; Seidl, Michael & Scheer, Manfred
  
• Novel synthetic route towards heteroleptic pnictogen-rich organometallic–inorganic coordination compounds. Dalton Transactions, 52(48), 18137-18142.
  Shelyganov, Pavel A.; Elsayed, Moussa Mehdi; Seidl, Michael; Zimmermann, Lisa; Menezes, da Silva Wagner & Scheer, Manfred
  
• Organometallic–Organic Hybrid Assemblies Featuring the Diantimony Complex [Cp2Mo2(CO)4(μ,η2‐Sb2)], AgI Ions and N‐Donor Molecules as Building Blocks. Chemistry – A European Journal, 29(35).
  Shelyganov, Pavel A.; Elsayed, Moussa Mehdi; Seidl, Michael & Scheer, Manfred
  
• Phase dependence and mechanical and thermal ductility of the luminescence properties of tetranuclear Cu(i) metallacycle assemblies stabilized by ditopic organo-pnictogen (P,As) ligands. Inorganic Chemistry Frontiers, 10(23), 6976-6989.
  Lecourt, Constance; Utrera, Melero Raquel; Schiller, Jana; Moutier, Florent; Dorcet, Vincent; Calvez, Guillaume; Poidevin, Corentin; Costuas, Karine; Scheer, Manfred & Lescop, Christophe
  
• Cu(I) Complexes Comprising tetrahedral Mo2E2 or Mo2PE units (E=P, As, Sb) as Chelating Ligands. Chemistry – A European Journal, 30(11).
  Mondal, Bijan & Scheer, Manfred
  
• High Temperature Irreversible Post-Synthetic Solid-State Transition Impacting the Luminescence Properties of Cu(I)-based 1D-Coordination Polymers. Adv. Optical Mater. 2024
  A. Schlachter, F. Moutier, R. Utrera Molero, J. Schiller, A. Mustafa Khalil, G. Calvez, M. Scheer, K. Costuas & Ch. Lescop
  
• High‐Temperature Solid‐State Post‐Synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers. Angewandte Chemie, 137(1).
  Schlachter, Adrien; Xu, Chendong; Schiller, Jana; Melero, Raquel Utrera; Kerneis, Sébastien; Calvez, Guillaume; Costuas, Karine; Scheer, Manfred & Lescop, Christophe
  
• Oligomer and Polymer: Self Assembly of [Cp*Fe(η5‐P5)] and Ag(I) Salts of Bulky Weakly Coordinating Anions. European Journal of Inorganic Chemistry, 27(23).
  Mondal, Bijan; Riesinger, Christoph; Fleischmann, Martin & Scheer, Manfred
  
• Pseudohalide Ions as Ligands to Tune Architecture and Luminescence of Polymetallic CU(I) Assemblies. Inorganic Chemistry, 63(14), 6370-6382.
  Lecourt, Constance; Hossain, Sayed Muktar; Xu, Chendong; Khalil, Ali Mustafa; Calvez, Guillaume; Triki, Smail & Lescop, Christophe
  
• Supramolecular compounds assembled from the heteroleptic tetrahedral complex [{CpMo(CO)2}2(μ,η2-AsSb)] and metal salts. Chemical Communications, 60(35), 4703-4706.
  Elsayed, Moussa Mehdi; Shelyganov, Pavel A.; Seidl, Michael; Zimmermann, Lisa & Scheer, Manfred