Interplay of ligand chirality and metal configuration in mononuclear complexes and in a coordination polymer of Cr(iii)

Abstract

In order to investigate the influence of ligand chirality on the configuration of the coordinated metal, five pseudooctahedral CrIJIII) complexes with one or two chelating R,R-1,2-diaminocyclohexane ligands have been synthesized. The mononuclear complexes ijCrIJR,R-chxn) 2 ClIJDMSO)]Cl 2 , ijCrIJR,R-chxn) 2 Cl 2 ]Cl, ijCrIJacacCN)IJR,R-chxn) 2 ]IJNO 3 ) 2 , ijCrIJacacCN) 2 IJR,R-chxn)]NO 3 , ijCrIJacacCN) 2 IJR,R-chxn)]PF 6 . (R,R-chxn = R,R-1,2-diaminocyclohexane; acacCN = deprotonated 3-cyanoacetylacetone and DMSO = dimethyl sulfoxide) have been obtained as crystalline solids, mostly solvates, and the potential chirality transfer from the enantiopure ligand to the configuration at the CrIJIII) center has been investigated. The cationic complex ijCrIJacacCN) 2 IJR,R-chxn)] + has been synthesized as exclusively Λ configured at the metal. In this complex, the dangling nitrile groups of the ditopic acacCN ligands may coordinate to AgIJI): the chiral-at-metal building block has thus been converted to the 2D network AgijCrIJacacCN) 2 IJR,R-chxn)] 2 IJPF 6 ) 3 under retention of the stereochemistry at CrIJIII). With respect to topology, the polycations in this mixed-metal coordination polymer correspond to two interpenetrated {4,4} nets. CrystEngCommThis journal is † Electronic supplementary information (ESI) available: Crystallographic information in CIF format; details concerning crystallization, structure solution and refinement of 1-4 and 6-8; hydrogen bonds in 1, 2, 6 and 8; displacement ellipsoid plots of asymmetric unit for 1-4 and 6-8; powder patterns for 1, 2, 4, 5, 6, 7 and 8. CCDC 1047808-1047814. For ESI and crystallographic data in CIF or other electronic format see

Marigold Flower‐Like Assemblies of Phosphorescent Iridium–Silver Coordination Polymers

“…The emission from triplet states in these coordination polymers is induced by the heavy atom effect of silver(I) ions and is ascribed to a mixture of an 3 MLCT transition, where electron is transferred from Ag(I) center to π * orbitals of the triazolates, and an 3 LLCT, cyanide‐to‐triazole charge transfer transition. 3D heterometallic coordination polymers and MOFs containing Ag(I) nodes were also reported by the groups of Englert, Hosseini, Mahon, Severin, Cohen, and Carlucci by reacting tritopic octahedral Fe(III), Al(III), Co(III), Cr(III), In(III), and Ga(III) metalloligands or ditopic tetrahedral Zn(II), Cu(II), and Pd(II) metalloligands, all containing 3‐cyano acetylacetonato units, with Ag + metal ions. These 3D heterometallic assemblies were found to be either nonemissive or no comment is made on their emission properties.…”

Absolute structure of the chiral pyrrolidine derivative (2S)-methyl (Z)-5-(2-tert-butoxy-1-cyano-2-oxoethylidene)pyrrolidine-2-carboxylate, a compound with low resonant scattering

“…The associated Cotton effect was well reproduced by our TDDFT calculations, thus confirming that our methodology was suitable. We hope to use enantiopure (1) in future experiments as a ditopic ligand with the additional possibility to transfer central chirality from the ligand to its coordination complexes (Wang et al, 2015). For both structures, data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction:…”

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

“…Within this pattern of catenation, the degree of interpenetration is equal to Z = d/l and this would allow prediction of the minimal diagonal length necessary to obtain a given Z. The presence of voluminous linkers and SBUs, guest molecules and/or counterions, or stronger interactions between different layers increases the value of l, reducing Z for a given value of the diagonal d. For example, six compounds with nitrile groups coordinated to Ag(I) (TUMBIO, 54 NEYRAK, 55 NEYREO, 55 NEYRIS, 55 OBELEN 56 and XOMGUC 57 ) have diagonal lengths of 15-20 Å, similar to other 3-fold interpenetrating dinitrile compounds, but they are only 2-fold and, consequently, have larger l of about 7.3-10 Å (Fig. S12 ‡).…”