Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt(CO)] Displaying a Defective Structure

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2022 Aug 3

PMID 35920640

Authors

Cristiana Cesari

Beatrice Berti

Tiziana Funaioli

Cristina Femoni

Maria Carmela Iapalucci

Daniele Pontiroli

Giacomo Magnani

Mauro Ricco

Marco Bortoluzzi

Federico Maria Vivaldi

Stefano Zacchini

Affiliations

Soon will be listed here.

Abstract

The molecular Pt nanocluster [Pt(CO)] () was obtained by thermal decomposition of [Pt(CO)] in tetrahydrofuran under a H atmosphere. The reaction of with increasing amounts of HBFEtO afforded the previously reported [Pt(CO)] () and [Pt(CO)] (). The new nanocluster was characterized by IR and UV-visible spectroscopy, single-crystal X-ray diffraction, direct-current superconducting quantum interference device magnetometry, cyclic voltammetry, IR spectroelectrochemistry (IR SEC), and electrochemical impedance spectroscopy. The cluster displays a cubic-close-packed Pt framework generated by the overlapping of four ABCA layers, composed of 3, 7, 11, and 6 atoms, respectively, that encapsulates a fully interstitial Pt tetrahedron. One Pt atom is missing within layer 3, and this defect (vacancy) generates local deformations within layers 2 and 3. These local deformations tend to repair the defect (missing atom) and increase the number of Pt-Pt bonding contacts, minimizing the total energy. The cluster is perfectly diamagnetic and displays a rich electrochemical behavior. Indeed, six different oxidation states have been characterized by IR SEC, unraveling the series of ( = 3-8) isostructural nanoclusters. Computational studies have been carried out to further support the interpretation of the experimental data.

References

Cattabriga E, Ciabatti I, Femoni C, Funaioli T, Iapalucci M, Zacchini S . Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt33(CO)38](2-) and the bcc [Pt40(CO)40](6-) Molecular Nanoclusters. Inorg Chem. 2016; 55(12):6068-79. DOI: 10.1021/acs.inorgchem.6b00607. View

Cesari C, Funaioli T, Berti B, Femoni C, Iapalucci M, Vivaldi F . Atomically Precise Ni-Pd Alloy Carbonyl Nanoclusters: Synthesis, Total Structure, Electrochemistry, Spectroelectrochemistry, and Electrochemical Impedance Spectroscopy. Inorg Chem. 2021; 60(21):16713-16725. PMC: 8564757. DOI: 10.1021/acs.inorgchem.1c02582. View

Femoni C, Iapalucci M, Longoni G, Tiozzo C, Zacchini S . An organometallic approach to gold nanoparticles: synthesis and X-ray structure of CO-protected Au21Fe10, Au22Fe12, Au28Fe14, and Au34Fe14 clusters. Angew Chem Int Ed Engl. 2008; 47(35):6666-9. DOI: 10.1002/anie.200802267. View

Barnett B, Rheingold A, Figueroa J . Monomeric Chini-Type Triplatinum Clusters Featuring Dianionic and Radical-Anionic π*-Systems. Angew Chem Int Ed Engl. 2016; 55(32):9253-8. DOI: 10.1002/anie.201604903. View

Jadzinsky P, Calero G, Ackerson C, Bushnell D, Kornberg R . Structure of a thiol monolayer-protected gold nanoparticle at 1.1 A resolution. Science. 2007; 318(5849):430-3. DOI: 10.1126/science.1148624. View

Nair A, Anoop A, Ahuja R, Pathak B . Role of atomicity in the oxygen reduction reaction activity of platinum sub nanometer clusters: A global optimization study. J Comput Chem. 2021; 42(27):1944-1958. DOI: 10.1002/jcc.26725. View

Jin R, Li G, Sharma S, Li Y, Du X . Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures. Chem Rev. 2020; 121(2):567-648. DOI: 10.1021/acs.chemrev.0c00495. View

Ciabatti I, Fabrizi de Biani F, Femoni C, Iapalucci M, Longoni G, Zacchini S . Metal Segregation in Bimetallic CoPd Carbide Carbonyl Clusters: Synthesis, Structure, Reactivity and Electrochemistry of [H Co Pd C (CO) ] (n=3-6). Chempluschem. 2020; 78(12):1456-1465. DOI: 10.1002/cplu.201300268. View

Li Y, Zhou M, Jin R . Programmable Metal Nanoclusters with Atomic Precision. Adv Mater. 2021; 33(46):e2006591. DOI: 10.1002/adma.202006591. View

10.

Cesari C, Bortoluzzi M, Femoni C, Iapalucci M, Zacchini S . One-pot atmospheric pressure synthesis of [HRu(CO)]. Dalton Trans. 2021; 50(27):9610-9622. DOI: 10.1039/d1dt01517f. View

11.

Jin R, Higaki T . Open questions on the transition between nanoscale and bulk properties of metals. Commun Chem. 2023; 4(1):28. PMC: 9814084. DOI: 10.1038/s42004-021-00466-6. View

12.

Imaoka T, Akanuma Y, Haruta N, Tsuchiya S, Ishihara K, Okayasu T . Platinum clusters with precise numbers of atoms for preparative-scale catalysis. Nat Commun. 2017; 8(1):688. PMC: 5613004. DOI: 10.1038/s41467-017-00800-4. View

13.

Bannwarth C, Ehlert S, Grimme S . GFN2-xTB-An Accurate and Broadly Parametrized Self-Consistent Tight-Binding Quantum Chemical Method with Multipole Electrostatics and Density-Dependent Dispersion Contributions. J Chem Theory Comput. 2019; 15(3):1652-1671. DOI: 10.1021/acs.jctc.8b01176. View

14.

Berti B, Cesari C, Femoni C, Funaioli T, Iapalucci M, Zacchini S . Redox active Ni-Pd carbonyl alloy nanoclusters: syntheses, molecular structures and electrochemistry of [NiPd(CO)] (x = 0.62), [NiPd(CO)] (x = 0.09) and [NiPd(CO)] (x = 0.27). Dalton Trans. 2020; 49(17):5513-5522. DOI: 10.1039/d0dt00337a. View

15.

Bortoluzzi M, Ciabatti I, Femoni C, Funaioli T, Hayatifar M, Iapalucci M . Homoleptic and heteroleptic Au(I) complexes containing the new [Co5C(CO)12](-) cluster as ligand. Dalton Trans. 2014; 43(25):9633-46. DOI: 10.1039/c4dt00854e. View

16.

Femoni C, Iapalucci M, Longoni G, Lovato T, Stagni S, Zacchini S . Self-assembly of [Pt(3n)(CO)(6n)]2- (n = 4-8) carbonyl clusters: from molecules to conducting molecular metal wires. Inorg Chem. 2010; 49(13):5992-6004. DOI: 10.1021/ic100547j. View

17.

Bortoluzzi M, Cesari C, Ciabatti I, Femoni C, Iapalucci M, Zacchini S . Reactions of Platinum Carbonyl Chini Clusters with Ag(NHC)Cl Complexes: Formation of Acid-Base Lewis Adducts and Heteroleptic Clusters. Inorg Chem. 2017; 56(11):6532-6544. DOI: 10.1021/acs.inorgchem.7b00665. View

18.

Cheng Q, Hu C, Wang G, Zou Z, Yang H, Dai L . Carbon-Defect-Driven Electroless Deposition of Pt Atomic Clusters for Highly Efficient Hydrogen Evolution. J Am Chem Soc. 2020; 142(12):5594-5601. DOI: 10.1021/jacs.9b11524. View

19.

Kruse H, Grimme S . A geometrical correction for the inter- and intra-molecular basis set superposition error in Hartree-Fock and density functional theory calculations for large systems. J Chem Phys. 2012; 136(15):154101. DOI: 10.1063/1.3700154. View

20.

Chakraborty I, Pradeep T . Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles. Chem Rev. 2017; 117(12):8208-8271. DOI: 10.1021/acs.chemrev.6b00769. View