Structural Regulation and Transformation of Oxalate-Bridged Polyoxo-Titanium Nanoclusters: Intercluster Docking Strategy and Polyiodides Induced Rearrangement.

Abstract

Although significant progress has been made in the synthetic and structural chemistry of polyoxo-titanium clusters (PTCs), the rational regulation of their geometric and electronic configurations is rather difficult. Meanwhile, it is also challenging to induce their systematic structural transformation, thereby customizing their physicochemical properties. In this work, we illustrate the intercluster docking strategy, which utilizes oxalates as multidentate ligands to connect and regulate the modular assembly of polynuclear Ti-O subunits into nanoclusters Ti24(μ3-O)26(μ2-O)4(OiPr)34(Oxal) (PTC-361), Ti28(μ4-O)2(μ3-O)28(μ2-O)8(OtBu)22(PA)12(Oxal) (PTC-362), Ti10(μ3-O)6(OtBu)14(PA)6(Oxal)2(tBC)2 (PTC-363), and Ti24(μ3-O)20(μ2-O)12(PA)12(Oxal)2(Hoxal)8(PyA)8 (PTC-364) (H2Oxal = oxalic acid; HOiPr = isopropanol; HOtBu = t-butanol; H2tBC = 4-tert-butylcatechol; HPA = propionic acid; and HPyA = 2-picolinic acid). Furthermore, the stepwise addition of iodine gives rise to polyiodide I3- to assist the controllable structure transformation of PTC-361 to [Ti12(μ-O)15(OiPr)17]I3 (PTC-365) and even to [Ti24(μ2-O)2(μ3-O)30(OiPr)30](I3)2 (PTC-366) with increasing polyiodide content. Moreover, modification with 4-tert-butylcatecholate as light absorbent material on the surface layers of PTCs and polyiodide I3- incorporation in PTCs expand their light response to the visible region and reduce their highest occupied molecular orbital-lowest unoccupied molecular orbital gaps. This work successfully develops an intercluster docking strategy and gives precise modulation on the geometry of nanoclusters as well as the optimization of their desired properties.