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. 2024 May 30;29(11):2566.
doi: 10.3390/molecules29112566.

Phenanthroline-Mediated Photoelectrical Enhancement in Calix[4]arene-Functionalized Titanium-Oxo Clusters

Jinle Hou  1 , Chen Huang  1 , Yuxin Liu  1 , Pengfei Fei  1 , Dongxu Zhang  1 , Konggang Qu  1 , Wenwen Zi  1 , Xianqiang Huang  1
Affiliations

Phenanthroline-Mediated Photoelectrical Enhancement in Calix[4]arene-Functionalized Titanium-Oxo Clusters

Jinle Hou et al. Molecules. .

Abstract

Incorporating two organic ligands with different functionalities into a titanium-oxo cluster entity simultaneously can endow the material with their respective properties and provide synergistic performance enhancement, which is of great significance for enriching the structure and properties of titanium-oxo clusters (TOCs). However, the synthesis of such TOCs is highly challenging. In this work, we successfully synthesized a TBC4A-functionalized TOC, [Ti2(TBC4A)2(MeO)2] (Ti2; MeOH = methanol, TBC4A = tert-butylcalix[4]arene). By adjusting the solvent system, we successfully introduced 1,10-phenanthroline (Phen) and prepared TBC4A and Phen co-protected [Ti2(TBC4A)2(Phen)2] (Ti2-Phen). Moreover, when Phen was replaced with bulky 4,7-diphenyl-1,10-phenanthroline (Bphen), [Ti2(TBC4A)2(Bphen)2] (Ti2-Bphen), which is isostructural with Ti2-Phen, was obtained, demonstrating the generality of the synthetic method. Remarkably, Ti2-Phen demonstrates good stability and stronger light absorption, as well as superior photoelectric performance compared to Ti2. Density functional theory (DFT) calculations reveal that there exists ligand-to-core charge transfer (LCCT) in Ti2, while an unusual ligand-to-ligand charge transfer (LLCT) is present in Ti2-Phen, accompanied by partial LCCT. Therefore, the superior light absorption and photoelectric properties of Ti2-Phen are attributed to the existence of the unusual LLCT phenomenon. This study not only deeply explores the influence of Phen on the performance of the material but also provides a reference for the preparation of materials with excellent photoelectric performance.

Keywords: DFT calculations; calix[n]arenes; crystal structure; photoelectric performance; titanium-oxo clusters.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Scheme 1
Scheme 1
Schematic diagram of the synthesis for Ti2, Ti2-Phen, and Ti2-Bphen. (TBC4A = tert-butylcalix[4]arene; iPrOH = isopropanol; Phen = 1,10-phenanthroline; Bphen = 4,7-diphenyl-1,10-phenanthroline).
Figure 1
Figure 1
(a) Crystal structure of Ti2. (b) Crystal structure of Ti2-Phen. (c) Crystal structure of Ti2-Bphen. (d) The coordination mode of TBC4A in Ti2. (e) The coordination mode of TBC4A in Ti2-Phen. Hydrogen atoms have been omitted for clarity. Color code: green for Ti, red for O, gray for C, and blue for N.
Figure 2
Figure 2
(a) PXRD patterns of Ti2 immersed in water solutions with pH values of 1, 7, and 11 for 24 h. (b) PXRD patterns of Ti2 immersed in common organic solvents for 24 h. (c) PXRD patterns of Ti2-Phen immersed in water solutions with pH values of 1, 7, and 11 for 24 h. (d) PXRD patterns of Ti2-Phen immersed in common organic solvents for 24 h.
Figure 3
Figure 3
(a) Solid-state UV-visible absorption spectra of TBC4A, Phen, Ti2, Ti2-Phen, and Ti2-Bphen. (b) Tauc plots of TBC4A, Phen, Ti2, Ti2-Phen, and Ti2-Bphen. (c) Transient photocurrent responses of Ti2, Ti2-Phen, and Ti2-Bphen under Xe lamp irradiation. (d) Electrochemical impedance spectroscopy (EIS) Nyquist plots of Ti2, Ti2-Phen, and Ti2-Bphen.
Figure 4
Figure 4
(a) Molecular orbital distribution of HOMO and LUMO for Ti2 based on DFT calculations. (b) Molecular orbital distribution of HOMO and LUMO for Ti2-Phen based on DFT calculations. (c) DOS plot for Ti2 based on DFT calculations. (d) DOS plot for Ti2-Phen based on DFT calculations.
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