Ionothermal Synthesis and Photoactivity of Ti_(17) and Ti_(19)-Oxo Clusters Functionalized by Sulfate and 1,10-Phenanthroline Ligands

In this study,we successfully synthesized two titanium-oxo clusters,namely Ti_(19)(μ_(3)-O)_(19)(μ_(2)-O)_(10)(1,10-phn)_(2)(OiPr)_(18)](PTC-178)and(EMIm)_(3)[Ti_(17)(μ_(4)-O)_(4)(μ_(3)-O)_(16)(μ_(2)-O)_(4)(SO_(4))_(3)(μ_(2)-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.

A ring-shaped 12-Ti-substituted poly(polyoxometalate):synthesis,structure,and catalytic properties

A new ring-shaped 12-Ti-substituted poly(polyoxometalate)(poly(POM)),K_(10)H_(15)[{K_(2)Na(H_(2)O)_(3)}@{(Ti_(2)O)_(2)(Ti_(4)O_(4))_(2)(A-α-1,3,5-GeW_(9)O_(36))_(2)(A-α-2,3,4-GeW_(9)O_(36))_(2)}]·45H_(2)O(1),has been made under hydrothermal conditions,showing the highest number of Ti centers in Keggin-type poly(POM)family to date.Its obvious feature is that two types of novel chiral trivacant[GeW_(9)O_(36)]^(14-)(A-α-1,3,5-GeW_(9)O_(36)and A-α-2,3,4-GeW_(9)O_(36))segments have been first discovered in POM chemistry,and four[GeW_(9)O_(36)]^(14-)segments are alternately connected by two Ti_(2)O and two Ti_(4)O_(4)cores to form a ring-shaped poly(POM),in which two types of linking modes,Ti_(2)O and Ti_(4)O_(4)bridging cores,are observed for the first time in POMs.The transformation of achiral precursors into chiral POM segments is of great significance for the POM synthetic chemistry.Furthermore,1 as a heterogeneous catalyst can effectively catalyze the oxidation of various thioethers and mustard gas simulant 2-chloroethyl ethyl sulfide(CEES).

An Organic–Inorganic Hybrid Material Based on Benzo[ghi]perylenetri-imide and Cyclic Titanium-Oxo Cluster for Efficient Perovskite and Organic Solar Cells

Perovskite and organic solar cells usually require electron-transport interlayers to efficiently transport electrons from the photoactive layer to the metal electrode.In general,pure organic or inorganic materials are applied into the interlayers,but organic–inorganic hybrid materials have been rarely reported for this application.In this work,we report using the first titanium-oxo cluster-based organic–inorganic hybrid as the interlayer material by introducing largeπ-conjugated benzo[ghi]perylenetriimides as an organic part via a simple ligand-exchange reaction.This new hybrid material showed excellent solubility,well-aligned energy levels,and excellent electron mobilities,enabling its great potential application as an interlayer in solar cells such as perovskite and organic solar cells,providing high power conversion efficiencies of>20%and 16%,respectively.Therefore,we claim that our present work introduces a new class of cluster-based organic–inorganic hybrid interlayer materials that exhibit promising application in organic electronics.