A new β-diketone ligand of nanometric length (HL), whose crystal structure shows a distance of 23 Å between two peripheral nitrile groups, has been employed with silver(I) to assemble 2D sql coordination networks showing the highest degree of interpenetration (Z) reported so far of 7- and 8-fold. Reacting HL with silver triflate and nitrate allowed to isolate and characterize the new compounds [Ag(HL)2](CF3SO3) (1) and [Ag(HL)2](NO3)·3H2O (2) in which only nitrile groups coordinate to tetrahedral silver atoms. X-ray diffraction analyses show the presence, in both compounds, of similar sql networks whose large rhombic windows (Ag…Ag edge length of more than 26 Å) allow the Z values of 7 and 8 for 1 and 2, respectively. Among the two species, the different degree of interpenetration is correlated to the conformational steric hindrance of the ligand, rather than the size of the rhombic windows, and it is ultimately a consequence of the nature of counterions. A Cambridge Structural Database (CSD) screening by ToposPro software shows that 1 and 2 are unique and, to the best of our knowledge, have the highest Z among interpenetrated sql 2D coordination networks (753 structures, for which the highest Z value is 5). The topologies of entanglement in the two structures have been also analysed and identified by their Extended Ring Net (ERNs) as the new patterns 28L1 for 1 and 32L1 for 2. We propose a correlation between Z and the diagonal length of the 4-rings by comparing 1 and 2 with 168 further structures showing the same type of interpenetration. Finally, the two CNs show interesting emissive properties at room temperature that are related to their different degree of interpenetration

Design and synthesis of new luminescent coordination networks of sql topology showing the highest degrees of interpenetration / D. Blasi, S. Quici, S. Orlandi, P. Mercandelli, A.V. Sokolov, E.V. Alexandrov, L. Carlucci. - In: CRYSTENGCOMM. - ISSN 1466-8033. - 24:30(2022 Aug 14), pp. 5474-5485. [10.1039/D2CE00884J]

Design and synthesis of new luminescent coordination networks of sql topology showing the highest degrees of interpenetration

D. Blasi
Primo
;
P. Mercandelli;L. Carlucci
Ultimo
2022

Abstract

A new β-diketone ligand of nanometric length (HL), whose crystal structure shows a distance of 23 Å between two peripheral nitrile groups, has been employed with silver(I) to assemble 2D sql coordination networks showing the highest degree of interpenetration (Z) reported so far of 7- and 8-fold. Reacting HL with silver triflate and nitrate allowed to isolate and characterize the new compounds [Ag(HL)2](CF3SO3) (1) and [Ag(HL)2](NO3)·3H2O (2) in which only nitrile groups coordinate to tetrahedral silver atoms. X-ray diffraction analyses show the presence, in both compounds, of similar sql networks whose large rhombic windows (Ag…Ag edge length of more than 26 Å) allow the Z values of 7 and 8 for 1 and 2, respectively. Among the two species, the different degree of interpenetration is correlated to the conformational steric hindrance of the ligand, rather than the size of the rhombic windows, and it is ultimately a consequence of the nature of counterions. A Cambridge Structural Database (CSD) screening by ToposPro software shows that 1 and 2 are unique and, to the best of our knowledge, have the highest Z among interpenetrated sql 2D coordination networks (753 structures, for which the highest Z value is 5). The topologies of entanglement in the two structures have been also analysed and identified by their Extended Ring Net (ERNs) as the new patterns 28L1 for 1 and 32L1 for 2. We propose a correlation between Z and the diagonal length of the 4-rings by comparing 1 and 2 with 168 further structures showing the same type of interpenetration. Finally, the two CNs show interesting emissive properties at room temperature that are related to their different degree of interpenetration
Settore CHIM/03 - Chimica Generale e Inorganica
PSRL219LPRAT_01 - Piano di Sostegno alla Ricerca 2015-2017 - Linea 2 "Dotazione annuale per attività istituzionali" (anno 2019) - PRATI, LAURA - PSR_LINEA2_ / Piano di sviluppo di ricerca - Dotazioni dipartimentali - Linea 2 - 2019
CAR_RIC14ESELL_M - Laboratorio multifunzionale e centro di formazione per la caratterizzazione e la sperimentazione preapplicativa di smart materials - SELLI, ELENA - CAR_RIC - Bandi Fondazione Cariplo - 2014
4-lug-2022
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/933769
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