Carboxylate Coordination Assisted Aggregation for Quasi‐Tetrahedral and Partial‐Dicubane [Cu4] Coordination Clusters. Issue 1 (25th January 2016)

• Record Type: Journal Article
• Authors: Mahapatra, Tufan Singha; Bauzá, Antonio; Dutta, Debodyuti; Mishra, Sabyashachi; Frontera, Antonio; Ray, Debashis
• Is Part Of: ChemistrySelect. Volume 1:Issue 1(2016)
• Page Start: 64
• Page End: 75
• Publication Date: 2016-01-25
• Subjects: Copper(II) carboxylate -- Aggregation -- Coordination modes -- Noncovalent interactions -- Density functional calculations; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201600006
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: The reaction of three copper(II) carboxylate (R = Me, Ph and H in RCO2 − ) salts in MeOH with H3 L resulted three [Cu4 ] aggregates: [Cu4 (μ4 ‐O)(μ‐H2 L)2 (μ1, 3 ‐O2 CCH3 )4 ] (1 ), [Cu4 (μ4 ‐O)(μ‐H2 L)2 (μ1, 3 ‐O2 CPh)(PhCO2 )3 ]⋅H2 O (2 ⋅H2 O), and [Cu4 (μ3 ‐OH)2 (μ‐H2 L)2 (μ1, 1 ‐HCO2 )2 (HCO2 )2 ]⋅2H2 O (3 ⋅2H2 O). Three different carboxylate groups showing varying coordination modes were responsible for the self‐aggregation of two ligand bound [Cu2 (H2 L)] 3+ units. The [Cu4 O] and [Cu4 (OH)2 ] cores were generated from water‐derived oxido and hydroxido nucleating groups to provide quasi‐tetrahedral and partial‐dicubane topologies. In complexes1 and2 ⋅2H2 O the μ1, 3 bridging mode of the carboxylate bridges were responsible for the entrapment of μ4 ‐O unit, whereas μ1, 1 bridge by formato groups resulted in trapping of two μ3 ‐OH units in complex3 ⋅2H2 O. Complex3 ⋅2H2 O is the first reported example of a μ1, 1 ‐formato bridged [Cu4 ] aggregate. Long range van der Waals forces, in presence of hydrogen bonding interactions, also play significant role in the [Cu4 ] aggregation process. These have been analyzed by DFT calculations and Hirshfeld surface analysis. Abstract : Control of copper(II) coordination aggregation by three different carboxylate groups have been provided quasi‐tetrahedral and partial‐dicubane [Cu4 ] complexes in [Cu4 (μ4 ‐O)(μ‐H2 L)2 (μ1, 3 ‐O2 CCH3 )4 ] (1 ), [Cu4 (μ4 ‐O)(μ‐H2 L)2 (μ1, 3 ‐O2 CPh)3 (PhCO2 )]⋅H2 O (2 ⋅H2 O) and [Cu4 (μ3 ‐OH)2 (μ‐H2 L)2 (μ1, 1 ‐HCO2 )2 (HCO2 )2 ]⋅2H2 O (3 ⋅2H2 O). The involvement and energetic contribution for long‐range interactions in hydrogen‐bonded assemblies and π–π stacking interactions have been analyzed by means of DFT calculations.