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Cluster-Containing Coordination Polymers Built Upon (Cu2I2S2)m Units (m = 2, 3) and ArSCH2C≡CCH2SAr Ligands: Is the Cluster Size Dependent Upon Steric Hindrance or Ligand Rigidity?

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Abstract

Two equivalents of CuI react with p-MeC6H4SCH2C≡CCH2SC6H4-p-Me (L2) to form the 2D network [(Cu4I4)(p-MeC6H4SCH2C≡CCH2SC6H4-p-Me)2] n (polymer 2) contrasting with the previously reported reaction with C6H5SCH2C≡CCH2SC6H5 (L1) which makes a 3D network [(Cu6I6)(C6H5SCH2C≡CCH2SC6H5)3] n (polymer 1) (2009, Dalton Trans. 948). The crystal structure of the latter polymer has been re-determined at 115, 155, 195, 235 and 275 K to study the impact of the recording temperature on the metric parameters, notably the Cu···Cu distances within the hexagonal prism Cu6I6 cluster. Steric hindrance between a 2D/(Cu4I4) versus 3D/(Cu6I6) appears to drive the selectivity. Upon using the ligand o-MeC6H4SCH2C≡CCH2SC6H4-o-Me (L3) with CuI, a new material (polymer 3) is formed but no X-ray structure determination was possible. From obvious steric considerations and the presence of a high energy emission characteristic of the well-known Cu4I4 cluster (absent in the Cu6I6 one), and the similarity in emission lifetime for both high and low energy emission of polymers 2 and 3, the nature of this polymer was proposed to be [(Cu4I4)(o-MeC6H4SCH2C≡CCH2SC6H4-o-Me)2] n .

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Acknowledgments

This research was supported by the CNRS, the Natural Sciences and Engineering Research Council of Canada (NSERC), le Fonds Québécois de la Recherche sur la Nature et les Technologies (FQRNT), the Centre d’ Etudes des Matériaux Optiques et Photoniques de l’Université de Sherbrooke (CEMOPUS), and the Agence National de la Recherche (ANR) for a grant of a Research Chair of Excellence.

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Authors and Affiliations

  1. Département de chimie, Université de Sherbrooke, Sherbrooke, QC, J1K 2R1, Canada

    Shawkat M. Aly & Pierre D. Harvey

  2. Institut UTINAM UMR CNRS 6213, Université de Franche-Comté, 25030, Besançon, France

    Abdoulaye Pam, Abderrahim Khatyr & Michael Knorr

  3. Institut de Chimie Moléculaire UMR CNRS 6302, Université de Bourgogne, 21078, Dijon, France

    Yoann Rousselin & Marek M. Kubicki

  4. Anorganische Chemie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, 44227, Dortmund, Germany

    Jonathan O. Bauer & Carsten Strohmann

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  1. Shawkat M. Aly
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Correspondence to Michael Knorr or Pierre D. Harvey.

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The authors dedicate this paper to the memory of Prof. Dwight A. Sweigart.

Shawkat M. Aly—On leave from Chemistry Department, Faculty of Science, Assiut University, Egypt.

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Aly, S.M., Pam, A., Khatyr, A. et al. Cluster-Containing Coordination Polymers Built Upon (Cu2I2S2)m Units (m = 2, 3) and ArSCH2C≡CCH2SAr Ligands: Is the Cluster Size Dependent Upon Steric Hindrance or Ligand Rigidity?. J Inorg Organomet Polym 24, 190–200 (2014). https://doi.org/10.1007/s10904-013-9984-9

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