Ionothermal Synthesis and Photoactivity of Ti₁₇ and Ti₁₉‐Oxo Clusters Functionalized by Sulfate and 1,10‐Phenanthroline Ligands

Abstract

Comprehensive SummaryIn this study, we successfully synthesized two titanium‐oxo clusters, namely Ti19(μ3‐O)19(μ2‐O)10(1,10‐phn)2(OiPr)18] (PTC‐178) and (EMIm)3[Ti17(μ4‐O)4(μ3‐O)16(μ2‐O)4(SO4)3(μ2‐OiPr)4(OiPr)13] (PTC‐179). These clusters were synthesized using an ionothermal reaction and possess similar nuclearity (Ti19 vs. Ti17) moieties. Additionally, we observed that these complexes exhibit varying activities for photocatalytic degradation of Methylene Blue (MB) dye and distinct photocurrent responses for photoelectrochemical studies due to their different surface‐decorated ligands. This study provides valuable insights into the design of Ti‐oxo molecular clusters with similar nuclearity but different surface environments, allowing for the establishment of critical structure‐property relationships. Furthermore, our research contributes to the exploration of sustainable synthetic methods for high nuclearity TOCs using ionic liquids.

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

“…(2) In the presence of TBC4A ligands, the introduction of Phen can further broaden the light absorption range of TOCs. In addition, previously reported Phen-functionalized TOCs are colorless and have light absorption limited to the ultraviolet region [56,57]. Therefore, the wider light absorption range of Ti2-Phen is attributed to the synergistic effect of TBC4A and Phen.…”

“…Due to the relatively weak affinity between N atoms and Ti, in previous reports, bifunctional ligands containing both N and O atoms were typically introduced into the synthetic system of TOCs [50,51]. Recently, 1,10-phenanthroline (Phen), as a typical bidentate nitrogen donor ligand and π-conjugated chromophore, has been employed to construct functional TOCs [52][53][54][55][56]. For instance, the Xuan group successfully synthesized phen-functionalized cocrystal TOCs and achieved the separation of purephase crystals by adjusting the synthesis conditions, which were then successfully applied to the photocatalytic sulfoxidation reaction [57].…”

Synthesis and Properties of Cobalt/Nickel-Iron-Antimony(III, V)-Oxo Tartrate Cluster-Based Compounds

“…Thus, it is crucial to solve the environmental pollution problems caused by these species [25][26][27]. In recent years, a number of scholars have utilized metal oxides with precise atomic structures as catalysts for photodegradation of organic dye wastewater [8,28,29]. On account of this, we investigated the photocatalytic degradation performance of compounds 2 and 4 as inhomogeneous reaction photocatalysts using methylene blue (MB) as a simulated pollutant.…”

Structural Chemistry of Titanium (IV) Oxo Clusters, Part 2: Clusters without Carboxylate or Phosphonate Ligands

“…Furthermore, four Ti 4 O 4 rings can be identified in the cage network, in addition to the Ti 2 O 2 and Ti 3 O 3 rings. The Ti 18 shell of Ti 19 O 29 (O i Pr) 18 (phen) 2 is very similarly structured [108] . A tetrahedral [TiO 4 ] unit in the cavity is bonded to four octahedrally coordinated Ti atoms of the shell by means of μ 3 ‐O.…”

“…The three layers are laterally expanded. The middle layer of the Ti [106b,107] Ti 17 O 24 (OiPr) 18 X 2 (X = anion of coumarine 343), [106b] [Ti 17 O 24 (OiPr) 17 (SO 4 ) 3 ] 3À [108] or several catecholato derivatives Ti 17 O 24 (OiPr) 20-x (catecholate) x (x = 1, 2, 4). [109] A carboxylato-substituted cluster of this type is also known, viz.…”