Inorganic Chemistry最新文献

{"title":"Pd-Based Multi-Site Catalysts for Selective CO2-to-Methanol Conversion","authors":"Shuang-long Zhou, Yu Dai, Qiang Song, Lina Lu, Xiao Yu","doi":"10.1021/acs.inorgchem.4c03789","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03789","url":null,"abstract":"Developing a multi-site Pd-based electrocatalyst for CO₂-to-C1 conversion with high performance and selectivity in the hydrogenation pathway for the CO₂ electroreduction reaction is both desirable and challenging. Here, we develop triple-site metallene (Pd₈₂Bi₁₁In₇), which can achieve an unprecedented Faraday efficiency of 72.6 ± 1% for methanol production. X-ray photoelectron spectroscopy analysis indicates that some electrons transfer from In and Bi to Pd inside Pd₈₂Bi₁₁In₇, forming local electron-rich Pd-site, local primary electron-deficient center In-site, and local secondary electron-deficient center Bi-site. Meanwhile, Pd₈₂Bi₁₁In₇ has stronger adsorption for *COOH and *CO, which avoids the generation of formic acid and CO. Moreover, Pd₈₂Bi₁₁In₇ reduces the potential determining step energy barrier and controls the hydrogenation path for direct methanol production. The synergistic effect of the triple-sites enables efficient CO₂ electroreduction to methanol.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Redistribution of Electron Density for Promoting CO2 Conversion Capacity","authors":"Changsong Shi, Ruiming Xu, Ting Suo, Xiang Shi, Shizhong Luo, Ruirui Yun","doi":"10.1021/acs.inorgchem.4c04169","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04169","url":null,"abstract":"There is a need to design substrate-supported catalysts for the heterogeneous fields, especially with large porosity, which can facilitate mass transport. Herein, aiming at enhancing the performance of CO₂ fixation, a hollow carbon sphere-supported catalyst of Fe_NPs/HCS (Fe_NPs, Fe nanoparticles; HCS, hollow carbon sphere) is facilely designed and fabricated. Excitingly, the experimental and calculation results reveal that Fe_NPs/HCS displays an ultrahigh activity with almost complete conversions in CO₂ cycloaddition, surpassing the performance of Fe_NPs/CS (CS, carbon sphere); this demonstrates that the HCS plays a key role, which may be attributed to the hollow structure tuning the electron density and enhancing the enrichment of the substrate and CO₂, consequently lowering the barrier associated with mass transfer. The work not only provides a novel strategy to construct an efficient catalyst but also proposes, for the first time, an electron redistribution tactic to influence the catalytic process for CO₂ cycloaddition.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841498","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activation and Functionalization of the Uranyl Ion by Electrochemical Reduction","authors":"Riddhi R. Golwankar, Małgorzata Z. Makoś, Nathalia Cajiao, Michael L. Neidig, Allen G. Oliver, Cynthia S. Day, Victor W. Day, Vassiliki-Alexandra Glezakou, James D. Blakemore","doi":"10.1021/acs.inorgchem.4c03349","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03349","url":null,"abstract":"Interconversion of the oxidation states of uranium enables separations and reactivity schemes involving this element and contributes to technologies for recycling of spent nuclear fuels. The redox behaviors of uranium species impact these processes, but use of electrochemical methods to drive reactions of molecular uranium complexes and to obtain molecular insights into the outcomes of electrode-driven reactions has received far less attention than it deserves. Here, we show that electro-reduction of the uranyl ion (UO₂²⁺) can be used to promote stepwise functionalization of the typically unreactive oxo groups with exogenous triphenylborane (BPh₃) serving as a moderate electrophile, avoiding the conventional requirement for a chemical reductant. Parallel electroanalytical, spectrochemical, and chemical reactivity studies, supported by spectroscopic findings and structural data from X-ray diffraction analysis on key reduced and borylated products, demonstrate that our electrochemical approach largely avoids undesired cross reactions and disproportionation pathways; these usually impact the multicomponent systems needed for uranyl functionalization chemistry. Joint computational studies have been used to map the changes associated with U–O activation and to quantify the free energy differences related to key reactions. Taken together, the results suggest that electrochemical methods can be used for selective interconversion of molecular actinide species, reminiscent of methods commonly employed in transition metal redox catalysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ca2+/Si4+ Modification of the (Gd,Lu)AG Garnet for Enhanced Broadband Cr3+ Luminescence of High Thermal Stability","authors":"Yun Wang, Zhiyuan Pan, Sihan Feng, Lijie Gao, Xuejiao Wang, Qi Zhu, Ji-Guang Li","doi":"10.1021/acs.inorgchem.4c04702","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04702","url":null,"abstract":"Near-infrared (NIR)-emitting phosphors with high quantum efficiency and thermal stability are crucial to NIR pc-LEDs. Garnet-structured (GdLuCa)(Al_4–<i>z</i>SiCr_<i>z</i>)O₁₂ (<i>z</i> = 0.01–0.2) and (Gd_2–<i>x</i>LuCa_<i>x</i>)(Al_{4.95–<i>x</i>}Si_<i>x</i>Cr_0.05)O₁₂ (<i>x</i> = 0.2–1.0) new phosphors with promising NIR luminescence under blue light excitation were designed and fabricated by a solid-state reaction in this work. It was analyzed that the Ca²⁺, Cr³⁺, and Si⁴⁺ ions would replace Gd³⁺ in [GdO₈], Al1 in [Al1O₆], and Al2 in [Al2O₄], respectively, and the optimal Cr³⁺ content is <i>z</i> = 0.05, above which concentration quenching would occur via an electric dipole–dipole interaction. Increasing Ca²⁺/Si⁴⁺ substitution up to <i>x</i> = 1.0 led to luminescence enhancement by a factor of up to 1.85 and internal/external quantum efficiency (%) increment from ∼25.9/10.7 to 63.4/27.5, and all of the phosphors showed excellent thermal stability (<i>I</i>_423 K/<i>I</i>_298 K ≥ 87.6%). The luminescence properties of Cr³⁺ were discussed in detail through systematic investigation of the effects of Cr³⁺ and Ca²⁺/Si⁴⁺ contents on the crystal structure, local coordination, and crystal field. With the NIR pc-LED device integrated from the optimal phosphor (<i>x</i> = 1.0) and a blue LED chip, electroluminescence manifested potential applications in night vision and medical diagnosis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multinuclear Antimony–Bismuth–Lanthanide Cluster-Connected Polyoxometalate for the Detection of 5-Hydroxyindoleacetic Acid via Luminescence","authors":"Chenyun Liu, Siyu Zhang, Yongchao Dai, Fan Wu, Jiancai Liu, Junwei Zhao","doi":"10.1021/acs.inorgchem.4c04233","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04233","url":null,"abstract":"The judicious selection and combination of multicomponents provide great potential for the further exploration of new polyoxometalate (POM) materials. Here, a delicate control on tungstate, Sb^III and Bi^III sources, Eu³⁺ ions, and organic molecules led to the discovery of a novel multimetal cluster-embedded POM [H₂N(CH₃)₂]₉Na₈H₅{[Eu₄(H₂O)₆Sb₄Bi₂W₂O₁₂](SbW₉O₃₃)₂(SbW₈O₃₁)₂}·78H₂O (<b>1</b>). The polyoxoanion of <b>1</b> was constructed from four in situ-formed [SbW₈O₃₁]^11– and [SbW₉O₃₃]^9– building blocks connected by two hexa-metallic [Eu₂(H₂O)₃Sb₂BiWO₆]⁹⁺ clusters, to be a rare member of Sb- and Bi-coexisting POM. The most impressive characteristic of <b>1</b> is the intricate [Eu₂(H₂O)₃Sb₂BiWO₆]⁹⁺ cluster linker, which contains a Sb^III–Bi^III coinserted [Sb₂BiWO₆]³⁺ core grasping one [Eu1(H₂O)₂]³⁺ cation and one [Eu2(H₂O)]³⁺ cation on both sides through Sb–O–Eu and Bi–O–Eu bonds. Functionalized by luminescence centers of Eu³⁺ ions, <b>1</b> can emit intense emission in water and be capable of detecting the biomarker of carcinoids, 5-hydroxyindoleacetic acid (5-HIAA) with a low limit of detection of 0.43 μM, high selectivity, and excellent anti-interference, as well as fast response (12 s). The high detectability of <b>1</b> for 5-HIAA is relevant to the underlying dynamic quenching and energy-transfer mechanism. In urine conditions, remarkable recognition of <b>1</b> for 5-HIAA and satisfactory recoveries were achieved, indicative of the possibility of <b>1</b> in detecting 5-HIAA in a real environment. This work reveals the special clustering effect of Sb^III and Bi^III atoms in the assembly of neoteric POM species and also promotes the application of POMs as potential diagnostic tool in the early detection of carcinoids.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Exploration of the Synergistic Effect of Phosphate and Amidoxime for Uranium Recovery from Seawater","authors":"Yi-Chen Huang, Cong-Zhi Wang, Qun-Yan Wu, Jian-Hui Lan, Chang-Ming Nie, Shu-Sen Chen, Yan Song, Hao Li, Wei-Qun Shi","doi":"10.1021/acs.inorgchem.4c03912","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03912","url":null,"abstract":"Highly selective extraction of uranium from seawater is currently extremely challenging. Although the amidoxime group (HAO) is the commonly used ligand in seawater uranium extraction, it also has strong binding capacity for vanadium ion. It has been shown that the introduction of phosphate groups into amidoxime-based adsorbents can improve the adsorption performance of materials through a synergistic effect between functional groups. In this work, we have systematically investigated the selective extraction behavior of the phosphate ligand (methylphosphonic acid, HL₁) for uranyl cation and the synergistic effect with amidoxime using density functional theory (DFT). The electron-donor-substituted derivatives of HL₁ (aminomethylphosphonic acid (HL₂) and methyl phosphate (HL₃)) were also considered. Not unexpectedly, the results show that introduction of HL₁ into the amidoxime-based adsorbents improves the extraction and selectivity for uranyl cations. This is mainly due to the fact that HL₁ is more likely to deprotonate, which promotes the dissociation of [UO₂(CO₃)₃]^4–, and the presence of the phosphate groups in the synergistic complexes alters the optimal coordination mode of VO₂⁺. In addition, the HL₂ and HL₃ ligands further improve the uranium extraction performance, especially for HL₃. This work provides guidelines for the rational design of sequestering ligands for uranium extraction from seawater.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"79 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tin-Chelated Trisphosphineoxide Scorpionate Rare-Earth Porphyrinate Complexes: Synthesis and Photophysical Properties","authors":"Da Jin, Cedric Uhlmann, Erik K. Schneider, Tim Seifert, Dominik Graf, Sergei Lebedkin, Patrick Weis, Manfred M. Kappes, Peter W. Roesky","doi":"10.1021/acs.inorgchem.4c04065","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04065","url":null,"abstract":"A series of seven-coordinated monoporphyrinate rare-earth(III) complexes featuring a novel tripodal tin-chelated trisphosphineoxide scorpionate ligand with the general formula [(TPP)Ln(PPh₂O)₃Sn] (Ln = Y, La, Dy, Er, Ho, Yb; TPP = 5,10,15,20-tetraphenylporphyrinate) were synthesized by reactions of the potassium tripodal scorpionate ligand [Sn(PPh₂O)₃K] with porphyrinate rare-earth metal chlorides [(TPP)LnCl(dme)] (Ln = Y, Dy, Er, Ho, Yb) or porphyrinate lanthanum borohydride [(TPP)LaBH₄(thf)₂]. The complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy, and ion mobility mass spectrometry. All complexes emit weak red TPP-based fluorescence, accompanied by near-infrared emission of Er, Ho (rather weak), and Yb (relatively intense with a quantum yield of 1% in dichloromethane solution) of the corresponding complexes. Despite the low intensity, the red fluorescence is characteristic (as referred to the parent free-base TPP) and can be used together with optical absorption for analytical evaluation. Similar photophysical properties can be expected for monoporphyrinate rare-earth metal complexes of other tripodal ligands with a similar binding to the (TPP)Ln moiety.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced Proton-Coupled Electron-Transfer Reactivity by a Mononuclear Nickel(II) Hydroxide Radical Complex","authors":"Daniel Ye, Tong Wu, Ankita Puri, David D. Hebert, Maxime A. Siegler, Michael P. Hendrich, Marcel Swart, Isaac Garcia-Bosch","doi":"10.1021/acs.inorgchem.4c03370","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03370","url":null,"abstract":"The synthesis, characterization, and reactivity of a NiOH core bearing a tridentate redox-active ligand capable of reaching three molecular oxidation states is presented in this paper. The reduced complex [LNiOH]^2– was characterized by single-crystal X-ray diffraction analysis, depicting a square-planar NiOH core stabilized by intramolecular H-bonding interactions. Cyclic voltammetry measurements indicated that [LNiOH]^2– can be reversibly oxidized to [LNiOH]⁻ and [LNiOH] at very negative reduction potentials (−1.13 and −0.39 V vs ferrocene, respectively). The oxidation of [LNiOH]^2– to [LNiOH]⁻ and [LNiOH] was accomplished using 1 and 2 equiv of ferrocenium, respectively. Spectroscopic and computational characterization suggest that [LNiOH]^2–, [LNiOH]⁻, and [LNiOH] are all Ni^II species in which the redox-active ligand adopts different oxidation states (catecholate-like, semiquinone-like, and quinone-like, respectively). The NiOH species were found to promote H-atom abstraction from organic substrates, with [LNiOH]⁻ acting as a 1H⁺/1e^– oxidant and [LNiOH] as a 2H⁺/2e^– oxidant. Thermochemical analysis indicated that [LNiOH] was capable of abstracting H atoms from stronger O–H bonds than [LNiOH]⁻. However, the greater thermochemical tendency of [LNiOH] reactivity toward H atoms did not align with the kinetics of the PCET reaction, where [LNiOH]⁻ reacted with H-atom donors much faster than [LNiOH]. The unique stereoelectronic structure of [LNiOH]⁻ (radical character combined with a basic NiOH core) might account for its enhanced PCET reactivity.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phosphorescent Chiral Cationic Binuclear Iridium(III) Complexes: Boosting the Circularly Polarized Luminescence Brightness","authors":"Pierre-Henri Lanoë, Christian Philouze, Florian Molton, Nicolas Vanthuyne, Debsouri Kundu, Mathias Delporte--Pebay, Jeanne Crassous, Camille Latouche, Frédérique Loiseau","doi":"10.1021/acs.inorgchem.4c04271","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04271","url":null,"abstract":"We report the synthesis and characterization of two chiral binuclear iridium(III) complexes (<b>ΛΛ</b> and <b>ΔΔ</b>) prepared from enantiopure building blocks [μ-Cl₂(Δ-Ir(C^N)₂)₂] and [μ-Cl₂(Λ-Ir(C^N)₂)₂]. These building blocks have been obtained by chiral preparative high-performance liquid chromatography of the neutral iridium(III) complex <b>Irpiv</b> (piv = 2,2,6,6-tetramethylheptane-3,5-dionate) followed by selective degradation of the ancillary ligand. For comparison purposes, we also synthesized a monomer (<b>IrL¹</b>) and a dimer (<b>Ir₂L²</b>, mixture). All the complexes exhibit similar emission properties, emitting in the orange-red region of the spectra with a good photoluminescence quantum yield (λ_max = 610–625 nm, Φ ∼ 25%, τ ∼ 800–900 ns). However, the <b>ΛΛ</b> and <b>ΔΔ</b> complexes are optically active, indicating that no isomerization occurred during the different synthetic steps, as evidenced by both the circular dichroism spectra and their circularly polarized luminescence (CPL). The capital gain of the dimers (<b>Ir₂L²</b>, <b>ΛΛ</b>, and <b>ΔΔ</b>) is a 4-fold brightness (<i>B</i>₃₈₀ = ε_380 nm × Φ) compared to the monomer (<b>IrL¹</b>) and the CPL brightness (<i>B</i>_CPL = <i>B</i>₃₈₀ × <i>g</i>_lum/2) of the binuclear complexes being among the highest reported to date for chiral iridium(III) complexes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832740","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-Assembled Tetrahedral [Cr^III₄L₆]¹²⁺ Cage Displaying Near-Infrared Spin-Flip Photoluminescence.","authors":"Yating Ye, Carlos M Cruz, Benjamin Doistau, Enrique Colacio, Claude Piguet, Juan Manuel Herrera, Juan-Ramón Jiménez","doi":"10.1021/acs.inorgchem.4c04180","DOIUrl":"10.1021/acs.inorgchem.4c04180","url":null,"abstract":"<p><p>The thermodynamically controlled self-assembly of bis-bidentate quaterpyridine ligand, L = 2,2':5',5″:2″,2‴-quaterpyridine, with Cr^II and subsequent oxidation to Cr^III yields the first photoluminescent tetrahedral [Cr^III₄L₆]¹²⁺ molecular cage. Single-crystal X-ray diffraction reveals the presence of two homochiral cages (ΛΛΛΛ and ΔΔΔΔ) in the unit cell that crystallize as a racemic mixture. Additionally, a PF₆ anion is observed inside the cavity, in line with isostructural cages built with Ni^II or Fe^II. Each corner of the polyhedron is occupied by weakly antiferromagnetically coupled {Cr(bipy)₃}³⁺ (bipy = 2,2'-bipyridine) patterns, as revealed by magnetometry. Upon light excitation in the UV-vis region, spin-flip luminescence from the ²E/²T₁ excited states with a maximum at 727 nm (13755 cm^-1) was detected at room temperature. The measured excited state lifetime of 183 μs is longer than the 102 μs recorded for the mononuclear [Cr(bipy)₃]³⁺ complex under anaerobic conditions, whereas the luminescence quantum yields are in the same order of magnitude and amount to 10^-2 %. The photoluminescence brightness, <i>B</i>, calculated using the maxima of the absorption spectra for both species, goes from 14 M^-1·cm^-1 for the mononuclear compound to 90 M^-1·cm^-1 for the tetrahedral cage. This 6-fold improvement is observed across the entire excitation wavelength range, and it is due to the incorporation of four light-harvester units in the molecular cage.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"23886-23893"},"PeriodicalIF":4.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142749486","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}