Structure Lattice-Dimensionality and Spectroscopic
Property Correlations in Novel Binary and Ternary Materials of Group
13 Elements with α‑Hydroxycarboxylic Benzilic Acid and
Phenanthroline
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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(C<sub>14</sub>H<sub>10</sub>O<sub>3</sub>)<sub>2</sub>](C<sub>3</sub>H<sub>5</sub>N<sub>2</sub>)·H<sub>2</sub>O (<b>1</b>), [Al(C<sub>14</sub>H<sub>11</sub>O<sub>3</sub>)<sub>3</sub>]·0.5C<sub>2</sub>H<sub>5</sub>OH·4.5H<sub>2</sub>O (<b>2</b>), [Ga(C<sub>14</sub>H<sub>11</sub>O<sub>3</sub>)<sub>3</sub>]·CH<sub>3</sub>OH·3H<sub>2</sub>O (<b>3</b>), [In(C<sub>14</sub>H<sub>11</sub>O<sub>3</sub>)<sub>4</sub>]·C<sub>3</sub>H<sub>5</sub>N<sub>2</sub>·C<sub>2</sub>H<sub>5</sub>OH·H<sub>2</sub>O (<b>4</b>), [Tl(C<sub>14</sub>H<sub>11</sub>O<sub>3</sub>)]<sub><i>n</i></sub> (<b>5</b>), [Tl<sub>2</sub>(C<sub>14</sub>H<sub>11</sub>O<sub>3</sub>)<sub>2</sub>(phen)<sub>2</sub>] (<b>6</b>), and [Tl(C<sub>14</sub>H<sub>11</sub>O<sub>3</sub>)(phen)(H<sub>2</sub>O)](C<sub>14</sub>H<sub>12</sub>O<sub>3</sub>)(phen)
(<b>7</b>). All materials were characterized by elemental analysis,
Fourier transform infrared spectroscopy, <sup>13</sup>C, <sup>11</sup>B, <sup>27</sup>Al, <sup>71</sup>Ga, and <sup>205</sup>Tl 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
