Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α-Hydroxycarboxylic Benzilic Acid and Phenanthroline

Abstract

To probe and understand the structural and coordinative flexibility of Group 13 ions with α-hydroxycarboxylic acids, leading to crystalline inorganic–organic hybrid materials with distinct lattice architecture, dimensionality, and spectroscopic properties, the systematic synthesis and physicochemical properties of binary and ternary B(III), Al(III), Ga(III), In(III), and Tl(I)-benzilic acid-(phenanthroline) systems were investigated in water–alcohol mixtures. Stoichiometric reactions of Group 13 ions with benzilic acid and phenanthroline (phen) afforded the new materials [B(C14H10O3)2](C3H5N2)·H2O (1), [Al(C14H11O3)3]·0.5C2H5OH·4.5H2O (2), [Ga(C14H11O3)3]·CH3OH·3H2O (3), [In(C14H11O3)4]·C3H5N2·C2H5OH·H2O (4), [Tl(C14H11O3)]n (5), [Tl2(C14H11O3)2(phen)2] (6), and [Tl(C14H11O3)(phen)(H2O)](C14H12O3)(phen) (7). All materials were characterized by elemental analysis, Fourier transform infrared spectroscopy, 13C, 11B, 27Al, 71Ga, and 205Tl cross-polarization/magic-angle spinning NMR, thermogravimetric analysis, luminescence, and single crystal X-ray diffraction. The nature of the benzilate ligand and phenanthroline in the chemical reaction mixtures with Group 13 ions led to the emergence of distinct lattice composition-dimensionality (1D-2D) correlations at the binary-ternary level, providing spectroscopic fingerprint identity to M(I,III)-coordination and luminescence activity. The interplay between the benzilate ligand, phenanthroline, and Group 13 ions, (a) reveals well-defined contributions of the chemical and structural factors influencing the arising binary and ternary interactions at the M(I) and M(III) oxidation levels, and (b) clarifies correlations between crystal-lattice architecture and dimensionality with unique heteronuclear solid-state NMR and optical property signatures in inorganic–organic hybrid materials.