Synthesis Of Clusters Research Articles

Two mixed-valent cerium oxo clusters: synthesis, structure, and self-assembly

Studies on cerium oxo clusters (CeOCs) are not only significant for understanding the redox and hydrolysis behaviors of Ce(III/IV) ions but also crucial for the rational synthesis of novel clusters and nanoceria with specific Ce(III)/Ce(IV) ratios. Here, two sets of reactions were conducted using cerium nitrate and H2O2-oxidized cerium nitrate, resulting in the formation of two distinct mixed-valent CeOCs [CeIII4CeIV10O14(OH)2(PhCO2)22(DMF)6] (Ce14) and [CeIII2CeIV22O28(OH)8(PhCO2)30(DMF)4] (Ce24C). These two clusters exhibit different structures and Ce(III)/Ce(IV) ratios, demonstrating the critical role of cerium oxidation states and the occurrence of redox reactions in cluster formation. Ce14 is the first tetradecanuclear CeOC with a novel structure, whereas Ce24C differed in its Ce(III)/Ce(IV) ratio, protonation levels of O atoms, and ligands from previously reported 24-nuclear CeOCs. Furthermore, various techniques were employed to investigate the formation process of these two clusters. X-ray photoelectron spectra (XPS) revealed that the white precipitates formed during the preparation of Ce14 contain Ce(III) ions, while the reddish-brown precipitates formed during the preparation of Ce24C contain a mixture of Ce(III) and Ce(IV) ions. These two precipitations were individually dissolved in N,N-Dimethylformamide (DMF). The evolution of solution color and ultraviolet-visible (UV-Vis) spectra over time revealed the gradual oxidation of partial Ce(III) ions by oxygen in the solution of the white precipitation. As Ce(IV) ions increased in this solution, time-resolved small angle X-ray scattering (SAXS) data demonstrated the self-assembly of the Ce14 clusters after 4 days. In contrast, SAXS data and UV-Vis spectra revealed the rapid assembly of Ce24C clusters within 2 h due to the initial coexistence of Ce(IV) and Ce(III) ions in the DMF solution of the reddish-brown precipitation. The continued reduction of partial Ce(IV) ions in this solution does not affect Ce24C clusters’ formation and stability. Our studies expand the family of CeOCs and enhance our understanding of the effects of cerium’s oxidation states on cluster formation.

Subnanometric Pt-W Bimetallic Clusters for Efficient Alkaline Hydrogen Evolution Electrocatalysis.

Rational design and synthesis of subnanometric bimetallic clusters (SBCs) within a narrow size distribution, along with achieving full SBCs exposure on supporting materials, are formidable challenges that must be overcome to realize potential applications. This work details a facile strategy to synthesize fully exposed PtW SBCs with an average size of 0.81 nm on the surface of spherical N-doped carbon (PtW/NC), which is underpinned by the electrostatic interactions between the negatively charged [H3PtW6O24]5- polyanions and the positively charged closed-pore metal-organic framework (MOF) [Zn5(OH)2(AmTRZ)6]2+. The PtW/NC exhibits significant electrocatalytic performance and stability for the alkaline hydrogen evolution reaction with an ultralow overpotential of 4 mV at 10 mA cm-2, a low Tafel slope of 29 mV dec-1, and a long-term electrolysis stability exceeding 140 h. The Pt mass activity of PtW/NC is 34 times higher than that of commercial 20 wt % Pt/C at the 100 mV overpotential. Both theoretical calculations and electrochemical measurements indicate that a synergistic effect between Pt and W is responsible for this notable catalytic performance. The synthetic approach outlined in this work can be applied to other MOFs and coordination networks that lack pores or have limited porosity.

Search for Thiol‐Protected Gold Clusters Doped with Different Elements Using Dendrimers

AbstractThe synthesis of thiol‐protected Au clusters MAu24(SR)18 containing different elements (M: different element, SR: thiol ligand) generally requires various steps. Therefore, the finding of a new MAu24(SR)18 cluster is not easy though it is necessary to take a great deal of effort to consider the synthesis. In this study, MAu24(SR)18 is searched for and attempted cluster synthesis using a dendrimer‐template method. It is also found that this method may be useful for exploring and discovering new clusters.

Disordered electron transfer: New forms of defective steroidogenesis and mitochondriopathy.

Most disorders of steroidogenesis, such as forms of congenital adrenal hyperplasia (CAH) are caused by mutations in genes encoding the steroidogenic enzymes and are often recognized clinically by cortisol deficiency, hyper- or hypo-androgenism, and/or altered mineralocorticoid function. Most steroidogenic enzymes are forms of cytochrome P450. Most P450s, including several steroidogenic enzymes, are microsomal, requiring electron donation by P450 oxidoreductase (POR); but several steroidogenic enzymes are mitochondrial P450s, requiring electron donation via ferredoxin reductase (FDXR) and ferredoxin (FDX). POR deficiency is a rare but well-described form of CAH characterized by impaired activity of 21-hydroxylase (P450c21, CYP21A2) and 17-hydroxylase/17,20-lyase (P450c17, CYP17A1); more severely affected individuals also have the Antley-Bixler skeletal malformation syndrome and disordered genital development in both sexes, and hence is easily recognized. The 17,20-lyase activity of P450c17 requires both POR and cytochrome b5 (b5), which promote electron transfer. Mutations of POR, b5, or P450c17 can cause selective 17,20-lyase deficiency. In addition to providing electrons to mitochondrial P450s, FDX and FDXR are required for the synthesis of iron-sulfur clusters, which are used by many enzymes. Recent work has identified FDXR mutations in patients with visual impairment, optic atrophy, neuropathic hearing loss and developmental delay, resembling the global neurologic disorders seen with mitochondrial diseases. Many of these patients have had life-threatening events or deadly infections, often without an apparent triggering event. Adrenal insufficiency has been predicted in such individuals but has only been documented recently. Neurologists, neonatologists and geneticists should seek endocrine assistance in evaluating and treating patients with mutations in FDXR.

Application of Hard and Soft Acid-base Theory to Construct Heterometallic Materials with Metal-oxo Clusters.

Heterometallic cluster-based materials offer the potential to incorporate multiple functionalities, leveraging the aggregation effects of clusters and translating this heterogeneity and complexity into unexpected properties that are more than just the sum of their components. However, the rational construction of heterometallic cluster-based materials remains challenging due to the complexity of metal cation coordination and structural unpredictability. This minireview provides insights into a general synthetic strategy based on Hard and Soft Acids and Bases (HSAB) theory, summarizing its advantages in the designed synthesis of discrete heterometallic clusters (intracluster assembly) and infinite heterometallic cluster-based materials (intercluster assembly). Furthermore, it emphasizes the potential to exploit the intrinsic properties of mixed components to achieve breakthroughs across a broad range of applications. The insights from this review are expected to drive the progress of heterometallic cluster-based materials in a controllable and predictable manner.

Application of Hard and Soft Acid‐base Theory to Construct Heterometallic Materials with Metal‐oxo Clusters

AbstractHeterometallic cluster‐based materials offer the potential to incorporate multiple functionalities, leveraging the aggregation effects of clusters and translating this heterogeneity and complexity into unexpected properties that are more than just the sum of their components. However, the rational construction of heterometallic cluster‐based materials remains challenging due to the complexity of metal cation coordination and structural unpredictability. This minireview provides insights into a general synthetic strategy based on Hard and Soft Acids and Bases (HSAB) theory, summarizing its advantages in the designed synthesis of discrete heterometallic clusters (intracluster assembly) and infinite heterometallic cluster‐based materials (intercluster assembly). Furthermore, it emphasizes the potential to exploit the intrinsic properties of mixed components to achieve breakthroughs across a broad range of applications. The insights from this review are expected to drive the progress of heterometallic cluster‐based materials in a controllable and predictable manner.

Dynamic stable Pt13 clusters anchored on isolated ZnOx nanorafts for efficient cycloparaffin dehydrogenation

Methylcyclohexane (MCH) has attracted wide attention as liquid organic hydrogen carriers for safe alternative and high gravimetric hydrogen density. Pt13 cluster with its fascinating structure exhibits excellent performance in cycloalkane dehydrogenation reactions accompanied by balanced C-H cleavage capability. However, the controllable synthesis of stable Pt13 clusters under reaction conditions remains challenging. Herein, we successfully synthesized low-coordinated Pt13 clusters anchored by isolated ZnOx nanorafts on silanol-rich self-pillared zeolite nanosheets (SP-S-1). In situ XAFS spectra combined with theoretical calculations revealed that Pt13 clusters exhibited strong interfacial Pt-Zn bonds and reduced d-band center through orbital hybridization (Zn 3d - Pt 5d), facilitating C-H bond cleavage and toluene desorption. The optimized catalyst exhibited superior MCH dehydrogenation activity and durability, achieving a hydrogen production rate of 3457.9 mmolH2 gPt−1 min−1 at 400 ˚C and maintaining stable for over 100 hours. This study precisely synthesizes dynamic stable Pt13 clusters and provides valuable insights into the dehydrogenation mechanism.

Impaired Iron-Sulfur Cluster Synthesis Induces Mitochondrial PARthanatos in Diabetic Cardiomyopathy.

Diabetic cardiomyopathy (DCM), a severe complication of diabetes, is characterized by mitochondrial dysfunction, oxidative stress, and DNA damage. Despite its severity, the intrinsic factors governing cardiomyocyte damage in DCM remain unclear. It is hypothesized that impaired iron-sulfur (Fe-S) cluster synthesis plays a crucial role in the pathogenesis of DCM. Reduced S-sulfhydration of cysteine desulfurase (NFS1) is a novel mechanism that contributes to mitochondrial dysfunction and PARthanatos in DCM. Mechanistically, hydrogen sulfide (H2S) supplementation restores NFS1 S-sulfhydration at cysteine 383 residue, thereby enhancing Fe-S cluster synthesis, improving mitochondrial function, increasing cardiomyocyte viability, and alleviating cardiac damage. This study provides novel insights into the interplay between Fe-S clusters, mitochondrial dysfunction, and PARthanatos, highlighting a promising therapeutic target for DCM and paving the way for potential clinical interventions to improve patient outcomes.

Vapor Infiltration Synthesis of Indium Sulfide Magic Size Cluster.

The energetically favorable formation of atomically precise clusters, known as magic size clusters, in the solution phase enables a precision nanoscale synthesis with exquisite uniformity. We report the synthesis of magic size clusters via vapor infiltration of atomic layer deposition precursors directly in a polymer thin film. Sequential infiltration of trimethylindium vapor and hydrogen sulfide gas into poly(methyl methacrylate) leads to the formation of clusters with uniform properties consistent with a magic size cluster─In6S6(CH3)6. While an increase in cluster size might be expected with additional sequential infiltration cycles of the reactive In and S precursors, uniform properties consistent with magic size clusters form in multiple polymers under a range of processing conditions. Ultraviolet-visible absorption spectra of In6S6(CH3)6 are largely independent of the number of sequential infiltration cycles and exhibit air stability, both of which are attributed to an energetically favorable synthetic pathway that is evaluated with density functional theory.

Reshoring concepts: definitions and a structured bibliometric review

PurposeThe aim of this paper is to clearly mark the clusters in the related literature using bibliometric analysis and draw useful implications for the academic research purposes especially in the stream of Supply Chain Management (SCM).Design/methodology/approachBy employing rigorous selection criteria, sample articles were selected for synthesizing and conducting a bibliometric analysis. This paper tries to identify the significance of the concept of reshoring with the aspect of SCM, operations, logistics etc. Starting from sample selection, systematic selection criteria has been used to generate the database, using Scopus. The sample size was 184. Using VOSViewer, statistical and graphical representations were generated for clusters in the literature that will be useful for judging the trends of research under shoring concepts.FindingsFindings show that unclear difference compared to other supply chain concepts obstructs further theory development within reshoring concepts. To address this challenge, the review categorizes themes and defines boundaries. Based on the analysis findings, this paper advocates for additional research in areas that are crucial but have received limited or no attention. Specifically, there is a need for action research on motivations, governance modes, and location selection concerning reshoring decisions.Research limitations/implicationsThis review has a few limitations. The absence of publications in other language, than English, may result in a significant loss of knowledge. This research paper cited a few relevant publications in the form of conference papers, industry reports, books, and book chapters. Nonetheless, they were excluded from the organized bibliometric audit. To further advance the knowledge in this field, exploratory longitudinal case studies will bring to focus the changes on manufacturing strategies using the shoring and reshoring stages.Practical implicationsA current example of this is a French company named Stil (Terzian, 2020) which brought its glass thermometer production back to its home after the unexpected closure of its suppliers from China. Another Italian firm has restarted production of disposal bio-degradable face masks after 15 years to compete with low-cost alternatives from China (Greco, 2020). Reshoring concepts are now under consideration of organizations including Boeing, Bosch, Phillips and more.Originality/valueTo the best of our knowledge, this represents one of the earliest efforts to conceptualize and define reshoring concepts, aiming to distinguish them from one another appropriately. To accomplish this, the earlier demarcated clusters precede this section’s classification of reshoring concepts illustrated in Table 8. Based on the synthesis of definitions and thematic clusters above, we have concluded the literature review in this emerging field. It is intended to contribute to theory development and practitioner support in reshoring decisions by clarifying the dimensions.

Synthesis and Photochemical Properties of Heterometallic Ti-Cu Ring Clusters Constructed from Myo-Inositol Ligand.

Incorporating heterometals into titanium-oxygen clusters represents an effective approach to adjusting the band gap and absorption properties. Herein, a family of heterometallic Ti-Cu clusters was synthesized under solvothermal conditions. The unique structural feature of these clusters is the formation of ring clusters with myo-inositol ligands serving as structure-directing ligands. The myo-inositol ligand, as a typical polyol ligand, demonstrates flexible and distinctive coordination modes capable of chelating up to eight transition metal ions simultaneously. Compounds 4 and 5 show significant absorption in the visible region, indicating that the incorporation of Cu ions can efficiently tune the band gap of titanium-oxygen clusters.

Constructing Electron-Rich Ru Clusters on Non-Stoichiometric Copper Hydroxide for Superior Biocatalytic ROS Scavenging to Treat Inflammatory Spinal Cord Injury.

Traumatic spinal cord injury (SCI) represents a complex neuropathological challenge that significantly impacts the well-being of affected individuals. The quest for efficacious antioxidant and anti-inflammatory therapies is both a compelling necessity and a formidable challenge. Here, in this work, the innovative synthesis of electron-rich Ru clusters on non-stoichiometric copper hydroxide that contain oxygen vacancy defects (Ru/def-Cu(OH)2), which can function as a biocatalytic reactive oxygen species (ROS) scavenger for efficiently suppressing the inflammatory cascade reactions and modulating the endogenous microenvironments in SCI, is introduced. The studies reveal that the unique oxygen vacancies promote electron redistribution and amplify electron accumulation at Ru clusters, thus enhancing the catalytic activity of Ru/def-Cu(OH)2 in multielectron reactions involving oxygen-containing intermediates. These advancements endow the Ru/def-Cu(OH)2 with the capacity to mitigate ROS-mediated neuronal death and to foster a reparative microenvironment by dampening inflammatory macrophage responses, meanwhile concurrently stimulating the activity of neural stem cells, anti-inflammatory macrophages, and oligodendrocytes. Consequently, this results in a robust reparative effect on traumatic SCI. It is posited that the synthesized Ru/def-Cu(OH)2 exhibits unprecedented biocatalytic properties, offering a promising strategy to develop ROS-scavenging and anti-inflammatory materials for the management of traumatic SCI and a spectrum of other diseases associated with oxidative stress.

Groundwater resistant gene accumulation in mining-agriculture complex zones: Insights from metagenomic analysis of subterranean mineral and terrestrial agricultural interactions

During the Mining-Agriculture Complex Areas, the mining and agriculture activities could lead to an excessive presence of sulfate content in the regional groundwater. Sulfate exhibits the potential to influence the positive accumulation of RGs, although its mechanisms remain inadequately explored. To address this gap, this study analyzed the RGs buildup mechanisms in the groundwater of the mining-agriculture complex area. Results showed a widespread presence of antibiotic resistance genes (ARGs) and metal resistance genes (MRGs), especially in coal-seams crevice groundwater. And iron and sulfur are primary environmental factors conducive to RGs accumulation through a synergistic interaction. Microbial annotation of gene sets sourced from coal-seams crevice groundwater samples unveiled part of sulfur-metabolizing microorganisms that were hosts of both ARGs and MRGs. Mechanistic insights revealed that iron may stimulates reactive oxygen species (ROS) generation, facilitating RGs accumulation, while adjusting sulfur metabolism and the synthesis of iron-sulfur clusters, thereby augmenting microbial growth which as predominant hosts of RGs, thereby intensifying the buildup of RGs.

Tetradentate NOO′O″ Schiff-Base Ligands as a Platform for the Synthesis of Heterometallic CdII-FeIII and CdII-CrIII Coordination Clusters

Tetradentate NOO′O″ Schiff-Base Ligands as a Platform for the Synthesis of Heterometallic CdII-FeIII and CdII-CrIII Coordination Clusters

Encapsulation of Ru nanoparticles within NaY zeolite for ammonia decomposition

Uniform and minuscule Ru particles confined in NaY zeolite (Ru@NaY) are prepared via a simple in situ synthesis technique. Transmission electron microscopy studies indicate that the Ru particles are encapsulated within the micropores of NaY zeolite and form a uniform size of 1.5–3.5 nm. Thanks to the effective confinement of Ru particles within the NaY zeolite, as well as the high concentration of B-5 sites and basic sites, the prepared Ru@NaY catalysts show excellent NH3 decomposition activity and highly efficient H2 formation. Notably, the 0.1Ru@NaY catalyst achieves a 92.7% NH3 conversion and a H2 formation rate of 690 mmol min−1·gRu−1 at 500 °C and GHSV = 9000 mLNH3·gcat−1·h−1 and shows outstanding stability throughout a 95-h lifetime test. The encapsulation synthesis of Ru clusters in zeolites endows the catalysts with exceptional catalytic activities and excellent stability, thus providing new prospects for the production of H2 from NH3 decomposition.

Structural Transformation of Metastable Two-Electron Superatom Au-Doped Cu-Rich Alloy Nanocluster.

The ability to fabricate bimetallic clusters with atomic precision offers promising prospects for elucidating the correlations between their structures and properties. Nevertheless, achieving precise control at the atomic level in the production of clusters, including the quantity of dopant, characteristic of ligands, charge state of precursors, and structural transformation, have remained a challenge. Herein, we report the synthesis, purification, and characterization of a new bimetallic hydride cluster, [AuCu11(H){S2P(OiPr)2}6(C≡CPh)3] (AuCu11H). The hydride position in AuCu11H was determined using DFT calculations. AuCu11H comprises a ligand-stabilized defective fcc Au@Cu11 cuboctahedron. AuCu11H is metastable and undergoes a spontaneous transformation through ligand exchange into the isostructural [AuCu11(Cl){S2P(OiPr)2}6(C≡CPh)3] (AuCu11Cl) and into the complete cuboctahedral [AuCu12{S2P(OiPr)2}6(C≡CPh)4]+ (AuCu12) through an increase in nuclearity. These structural transformations were tracked by NMR and mass spectrometry.

One-pot synthesis and chiroptical activity of single Au-atom doped AuAg28 clusters protected by water-soluble chiral monothiol N‑acetyl‑(S)‑penicillamine (S-NAP)

Physicochemical properties of atomically precise metal clusters can be modulated by incorporating different metal atoms. In this article, successful one-pot synthesis of single Au-atom doped chiral AuAg28 clusters protected by water-soluble N‑acetyl‑(S)‑penicillamine (=S-NAP) is reported. The reduction of Ag and Au ions at 0 °C in the presence of S-NAP and triphenylphosphine (TPP) using tetramethylammonium borohydride (TMAB) is crucial. Importantly, upon doping of an Au atom to the monometallic Ag29 cluster, which improves the cluster stability, the chiroptical activity or maximum anisotropy factor of the bimetallic AuAg28 cluster is enhanced as compared to that of the monometallic species, which can be due to an increase in the rotatory strength that is probably brought about by the increased contribution of optical transition associated with helically-arranged surface shell layers. Such chiroptical behaviors suggest that the Au dopant position in the bimetallic cluster is not fluxional but rigid. Then the present results will help design some heteroatom-doped silver clusters with excellent chiroptical properties.

MTORC1 Signaling Inhibition Modulates Mitochondrial Function in Frataxin Deficiency.

Lysosomes regulate mitochondrial function through multiple mechanisms including the master regulator, mechanistic Target of Rapamycin Complex 1 (mTORC1) protein kinase, which is activated at the lysosomal membrane by nutrient, growth factor and energy signals. mTORC1 promotes mitochondrial protein composition changes, respiratory capacity, and dynamics, though the full range of mitochondrial-regulating functions of this protein kinase remain undetermined. We find that acute chemical modulation of mTORC1 signaling decreased mitochondrial oxygen consumption, increased mitochondrial membrane potential and reduced susceptibility to stress-induced mitophagy. In cellular models of Friedreich's Ataxia (FA), where loss of the Frataxin (FXN) protein suppresses Fe-S cluster synthesis and mitochondrial respiration, the changes induced by mTORC1 inhibitors lead to improved cell survival. Proteomic-based profiling uncover compositional changes that could underlie mTORC1-dependent modulation of FXN-deficient mitochondria. These studies highlight mTORC1 signaling as a regulator of mitochondrial composition and function, prompting further evaluation of this pathway in the context of mitochondrial disease.

Protocellular Heme and Iron-Sulfur Clusters.

ConspectusCentral to the quest of understanding the emergence of life is to uncover the role of metals, particularly iron, in shaping prebiotic chemistry. Iron, as the most abundant of the accessible transition metals on the prebiotic Earth, played a pivotal role in early biochemical processes and continues to be indispensable to modern biology. Here, we discuss our recent contributions to probing the plausibility of prebiotic complexes with iron, including heme and iron-sulfur clusters, in mediating chemistry beneficial to a protocell. Laboratory experiments and spectroscopic findings suggest plausible pathways, often facilitated by UV light, for the synthesis of heme and iron-sulfur clusters. Once formed, heme displays catalytic, peroxidase-like activity when complexed with amphiphiles. This activity could have been beneficial in two ways. First, heme could have catalytically removed a molecule (H2O2) that could have had degradative effects on a protocell. Second, heme could have helped in the synthesis of the building blocks of life by coupling the reduction of H2O2 with the oxidation of organic substrates. The necessity of amphiphiles to avoid the formation of inactive complexes of heme is telling, as the modern-day electron transport chain possesses heme embedded within a lipid membrane. Conversely, prebiotic iron-sulfur peptides have yet to be reported to partition into lipid membranes, nor have simple iron-sulfur peptides been found to be capable of participating in the synthesis of organic molecules. Instead, iron-sulfur peptides span a wide range of reduction potentials complementary to the reduction potentials of hemes. The reduction potential of iron-sulfur peptides can be tuned by the type of iron-sulfur cluster formed, e.g., [2Fe-2S] versus [4Fe-4S], or by the substitution of ligands to the metal center. Since iron-sulfur clusters easily form upon stochastic encounters between iron ions, hydrosulfide, and small organic molecules possessing a thiolate, including peptides, the likelihood of soluble iron-sulfur clusters seems to be high. What remains challenging to determine is if iron-sulfur peptides participated in early prebiotic chemistry or were recruited later when protocellular membranes evolved that were compatible with the exploitation of electron transfer for the storage of energy as a proton gradient. This problem mirrors in some ways the difficulty in deciphering the origins of metabolism as a whole. Chemistry that resembles some facets of extant metabolism must have transpired on the prebiotic Earth, but there are few clues as to how and when such chemistry was harnessed to support a (proto)cell. Ultimately, unraveling the roles of hemes and iron-sulfur clusters in prebiotic chemistry promises to deepen our understanding of the origins of life on Earth and aids the search for life elsewhere in the universe.

Auxiliary ligand-induced synthesis of ferrocene-sensitized titanium-oxo clusters with broad light absorption and excellent photoelectric properties

The rational design and construction of polyoxotitanium clusters with outstanding photoelectrochemical activity represents a significant challenge in the field. Herein, employing ferrocene as a photosensitizer and incorporating diverse auxiliary ligands, we have successfully constructed a family of structurally varied ferrocene-sensitized polyoxotitanium clusters, formulated as Ti3 (μ3-O) (Fcc)2(OiPr)8 (Ti3Fcc-1, Fcc = ferrocenecarboxylic acid), Ti3 (μ3-O) (Fcc) (L1) (OiPr)8 (Ti3Fcc-2, L1 = 6-amino-m-toluenesulfonic acid), Ti6 (μ3-O)2 (μ2-O) (Fcc)2 (L2)2(OiPr)10 (Ti6Fcc-1, L2 = salicylhydroxamic acid), Ti6 (μ3-O)4(Fcc)2 (L3)2(OiPr)10 (Ti6Fcc-2, L3 = diisopropanolamine), and Ti8 (μ3-O)4(Fcdc)4 (L4)2(OiPr)10 (Ti8Fcdc, Fcdc = 1,1-ferrocenedicarboxylic acid, L4 = triisopropanolamine). The incorporation of auxiliary groups can effectively regulate the structure of ferrocene-functionalized polyoxotitanium clusters, resulting in a gradual growth of the cluster core from Ti3 to Ti6, and ultimately reaching Ti8. Moreover, these titanium-oxo clusters exhibit displayed enhanced visible light absorption and narrow bandgaps, which are primarily attributed to the charge transport from Fcc/Fcdc and ancillary groups to the cluster core. These Ti-oxo clusters were also used as electrode precursors for investigating their photoelectric behaviors and exhibited clear photocurrent responses. This work not only expands ferrocene-sensitized titanium-oxo clusters library, but also provides guidance for the rational design and controllable construction on titanium-based photoactive materials.