Macedonian Source

Translated title of the contribution: Spiroconjugation over a boron atom: Facile synthesis, structures and vibrational spectra of crystalline 1,3-disubstituted (propen-1,3-diolato)(oxalato)boron molecules

Pance Naumov, Minjas Zugik, Albert Lee, Seik Weng Ng

    Research output: Contribution to journalArticle

    Abstract

    Preparation of single crystals of spiroconjugated bis-chelated boron compounds containing ligands such as propen-1,3-diolates and oxalate, for application as lasing materials in dye laser technology, is burdened by their insolubility in organic solvents and the high melting temperatures. In this work, on the example of (diphenylpropen-1,3-diolato)(oxalato)boron (1) it is demonstrated that the solvothermal method can be successfully applied as facile, convenient and fairly inexpensive method to overcome the difficulties with preparation of such materials in single crystalline form directly from boric acid and the ligands. Solid-state IR spectra (recorded at room temperature and low temperature) and Raman spectra (recorded at room temperature) and equilibrium molecular geometries of 1 and three other disubstituted β-ketoboron molecules [RC(O)CHC(O)R'](O2CCO2)B (R = R' = t-butyl, 2; R = methyl, R' = phenyl, 3; R = R' = 2-pyridyl, 4) in the ground electronic states were analyzed in detail, based on HF SCF (HF/3-21G, HF/6-31G), MP2 (MP2/6-31G) and DFT (B3LYP/6-31G) calculations. Minima with spiro-chelated tetrahedral (sp3) BO4 or trigonal-planar (sp2) BO3 coordination were located on the potential energy hypersurfaces for all systems. The tetrahedral structures are more stable relative to the trigonal structures (for example, ~37 kcal mol-1 in the case of 2), accounting for the observation that they represent the actual conformers in the solid state. Vibrational criteria for spectroscopic distinction between trigonal and tetrahedral boron-oxygen coordination geometry are presented.

    Original languageLithuanian
    Pages (from-to)55-77
    Number of pages23
    JournalMacedonian Journal of Chemistry and Chemical Engineering
    Volume28
    Issue number1
    StatePublished - Nov 6 2009

    Fingerprint

    Boron
    Vibrational spectra
    Crystalline materials
    Atoms
    Molecules
    Boron Compounds
    Ligands
    Boron compounds
    Boric acid
    Dye lasers
    Oxalates
    Geometry
    Electronic states
    Potential energy
    Discrete Fourier transforms
    Organic solvents
    Temperature
    Melting point
    Raman scattering
    Solubility

    Keywords

    • Ab initio calculations
    • Boron
    • Laser dyes
    • Nonlinear materials
    • Organoboron compounds
    • Solvothermal synthesis
    • Spiroconjugation
    • Spirointeraction
    • Vibrational spectra

    ASJC Scopus subject areas

    • Chemistry(all)
    • Chemical Engineering(all)

    Cite this

    Naumov, P., Zugik, M., Lee, A., & Weng Ng, S. (2009). Macedonian Source. Macedonian Journal of Chemistry and Chemical Engineering, 28(1), 55-77.

    Macedonian Source. / Naumov, Pance; Zugik, Minjas; Lee, Albert; Weng Ng, Seik.

    In: Macedonian Journal of Chemistry and Chemical Engineering, Vol. 28, No. 1, 06.11.2009, p. 55-77.

    Research output: Contribution to journalArticle

    Naumov, P, Zugik, M, Lee, A & Weng Ng, S 2009, 'Macedonian Source', Macedonian Journal of Chemistry and Chemical Engineering, vol. 28, no. 1, pp. 55-77.
    Naumov P, Zugik M, Lee A, Weng Ng S. Macedonian Source. Macedonian Journal of Chemistry and Chemical Engineering. 2009 Nov 6;28(1):55-77.
    Naumov, Pance ; Zugik, Minjas ; Lee, Albert ; Weng Ng, Seik. / Macedonian Source. In: Macedonian Journal of Chemistry and Chemical Engineering. 2009 ; Vol. 28, No. 1. pp. 55-77.
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    KW - Spirointeraction

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