Conductive wires of sub-micrometer width made from platinum-carbonyl clusters have been fabricated by solution-infilling of microchannels as in microinject molding in capillaries (MIMIC). The process is driven by the liquid surface tension within the micrometric channels followed by the precipitation of the solute. Orientation of supramolecular crystalline domains is imparted by the solution confinement combined with unidirectional flow. The wires exhibit ohmic conductivity with a value of 0.2 S/cm that increases, after thermal decomposition of the platinum-carbonyl cluster precursor to Pt, to 35 S/cm.
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http://dx.doi.org/10.1021/ja074104m | DOI Listing |
J Chem Phys
November 2024
College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, People's Republic of China.
Vibronic coherence has been studied for years, but direct comparisons between the rich experimental features and theory remain rare. In this work, we investigate the vibronic coherent quantum beat of a four-layer platinum carbonyl cluster [Pt3(CO)6]42- in a solution utilizing femtosecond vis-pump/vis-probe transient absorption spectroscopy. By varying the excitational wavelength, quantum beats coupled to either the electronic ground state or the excited state are selectively prepared.
View Article and Find Full Text PDFInorg Chem
August 2022
Dipartimento di Chimica Industriale "Toso Montanari", Università di Bologna, Viale Risorgimento 4, Bologna 40136, Italy.
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.
View Article and Find Full Text PDFNanoscale
March 2022
Univ Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR) - UMR 6226, F 35000 Rennes, France.
Although the chemistry of carbonyl-protected platinum nanoclusters is well established, their bonding mode remains poorly understood. In most of them, the average Pt oxidation state is zero or slightly negative, leading to the apparent average configuration 5d 6s ( = 0 or very small) and the apparent conclusion that metal-metal bonding cannot arise from the completely filled 5d shell nor from the empty (or almost empty) 6s orbitals. However, DFT calculations show in fact that in these species the actual average configuration is 5d 6s, which provides to the whole cluster a significant total number of 6s electrons that ensures metal-metal bonding.
View Article and Find Full Text PDFDalton Trans
March 2018
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
The reactions of [Pt3n(CO)6n]2- (n = 2-5) homoleptic Chini-type clusters with increasing amounts of 1,3,5-triaza-7-phosphaadamantane (PTA) result in the stepwise substitution of one terminal CO ligand per Pt3 triangular unit up to the formation of [Pt3n(CO)5n(PTA)n]2- (n = 2-5). Competition between the nonredox substitution with retention of the nuclearity and the redox fragmentation to afford lower nuclearity heteroleptic Chini-type clusters is observed as a function of the amount of PTA and the nuclearity of the starting cluster. Because of this, [Pt12(CO)20(PTA)4]2- and [Pt15(CO)25(PTA)5]2- are more conveniently obtained via the oxidation of [Pt9(CO)15(PTA)3]2-.
View Article and Find Full Text PDFInorg Chem
June 2017
Dipartimento di Chimica Industriale "Toso Montanari″, University of Bologna, Viale Risorgimento 4, I-40136 Bologna Italy.
The reactions of anionic platinum carbonyl Chini clusters [Pt(CO)] [n = 2 (1), 3 (2), 4 (3)] with Ag(IPr)Cl [IPr = CNH(CHPr)] afford the neutral acid-base Lewis adducts [Pt(CO)(AgIPr)] (4) and [Pt(CO)(AgIPr)] (5). These are thermally transformed into the homometallic heteroleptic neutral cluster [Pt(CO)(IPr)] (6). Alternatively, 6 can be obtained from the reactions of 1-3 with an excess of the free IPr carbene ligand.
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