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Triphenylamine-Based Bis(β-Diketones) for Construction of Supramolecular Copper(II) Complexes

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Abstract

Two new bis(β-diketone) ligands based on triphenylamine have been prepared and crystallized. Treatment of 4,4′-diformyltriphenylamine with two phospholenes (2,2,2-trimethoxy-4,5-dimethyl-1,3,2-dioxaphospholene and 2,2,2-trimethoxy-4,5-diethyl-1,3,2-dioxaphospholene) afforded the bis(β-diketones) triphenylaminebis(2,4-pentanedione) (tpbaH2, 1); and triphenylaminebis(3,5-heptanedione) (tpbprH2, 2) as white solids. X-ray analysis of 1 and 2 shows that they are in the enol form. Also, their triphenylamine moieties have a chiral “propeller” shape; the centrosymmetric structures contain equal numbers of the two enantiomeric propellers. Reaction of 1 and 2 with [Cu(NH3)4]2+(aq) yielded dark-green solids. The Cu complex of 1 was insoluble in common solvents, but that of 2, Cu4(tpbpr)4 (3), is soluble in dichloromethane and chloroform. 3 is assigned the cyclic tetrameric structure Cu4(tpbpr)4 based on ESI–MS and microanalytical data. This is similar to the copper(II) β-diketonate molecular squares reported previously from our group. Molecular modeling indicates that Cu4(tpbpr)4 has Cu···Cu distances of ca. 21 Å, as compared to ca. 14 Å in the previous molecular squares.

Graphical Abstract

Crystal structures of two new bis(β-diketones) are reported, which are likely to form large supramolecular structures on reaction with metal ions such as Cu2+.

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Data availability

The X-ray datasets generated and analyzed during the current study are available via the Cambridge Structural Database (https://www.ccdc.cam.ac.uk/structures/), using the CCDC deposition numbers in Table 1.

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Acknowledgements

This research was supported in part by the Office of Basic Energy Sciences, Department of Energy, USA (Grant No. DE-FG02-01ER15267), and by the LSU West Professorship. We thank the Louisiana Board of Regents for support of the X-ray diffractometers.

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Authors and Affiliations

  1. Department of Chemistry, Louisiana State University, Baton Rouge, LA, 70803, USA

    Jackson K. Cherutoi, Frank R. Fronczek & Andrew W. Maverick

  2. Department of Chemistry and Biochemistry, Moi University, P.O. Box 3900, Eldoret, 30100, Kenya

    Jackson K. Cherutoi

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  1. Jackson K. Cherutoi
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  3. Andrew W. Maverick
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All authors contributed to the study conception, design, material preparation, and data analysis. The first draft of the manuscript was written by JKC. All authors commented on the different versions of the manuscript, and read and approved the final version.

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Correspondence to Jackson K. Cherutoi or Andrew W. Maverick.

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Cherutoi, J.K., Fronczek, F.R. & Maverick, A.W. Triphenylamine-Based Bis(β-Diketones) for Construction of Supramolecular Copper(II) Complexes. J Chem Crystallogr 53, 475–482 (2023). https://doi.org/10.1007/s10870-023-00986-0

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