NDLI: Molybdenum–molybdenum quadruple bonds supported by 9,10-anthraquinone carboxylate ligands. Molecular, electronic, ground state and unusual photoexcited state properties

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Molybdenum–molybdenum quadruple bonds supported by 9,10-anthraquinone carboxylate ligands. Molecular, electronic, ground state and unusual photoexcited state properties

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Chemical Science Vol - 5 Issue - 6

Chemical Science Vol - 5 Issue - 5

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Chemical Science Vol - 5 Issue - 3

Chemical Science Vol - 5 Issue - 2

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Chemical Science Vol -1

Molybdenum–molybdenum quadruple bonds supported by 9,10-anthraquinone carboxylate ligands. Molecular, electronic, ground state and unusual photoexcited state properties

Content Provider	Royal Society of Chemistry (RSC)
Author	Durr, Christopher B. Spilker, Thomas F. Lewis, Sharlene A. Brown-Xu, Samantha E. Chisholm, Malcolm H. Young, Philip J.
Copyright Year	2014
Abstract	The preparation of trans-Mo2(TiPB)2(O2C-2-AnQ)2, I, and Mo2(DAniF)3(O2C-2-AnQ), II, where, O2C-2-AnQ = 9,10-anthraquinone-2-carboxylate, TiPB = 2,4,6-triisopropylbenzoate and DAniF = N,N′-di-(p-anisyl)formamidinate are described together with electronic structure calculations employing density functional theory on model compounds. Compounds I and II have been further characterized by 1H NMR spectroscopy, MALDI-TOF mass spectrometry, electrochemical studies, UV-vis-NIR and steady state emission spectroscopy, time-resolved (fs and ns) transient absorption and infrared spectroscopy. Compound II has been structurally characterized by a single crystal X-ray crystallography study. Both compounds show metal-to-ligand charge transfer transitions, 1MLCT, corresponding to Mo2 δ to L π* (L = O2C-2-AnQ) and have S1 states with relatively long lifetimes (τI ∼ 8 ps; τII ∼ 2 ps). Femtosecond time-resolved IR studies, fs-TRIR indicate that for I, despite its relatively small HOMO–LUMO gap, and II the negative charge in the S1 state resides on one anthraquinone carboxylate ligand. For II, fs-TRIR spectroscopy detects the Mo23δδ* state with τ ∼ 100 ns despite the presence of a lower energy 3MLCT state. This, together with earlier findings indicates a significant kinetic barrier to the interconversion of MLCT and Mo2 δδ* states.
Starting Page	2657
Ending Page	2666
Page Count	10
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	5
Issue Number	7
Journal	Chemical Science
DOI	10.1039/c4sc00341a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	X-ray crystallography Spectroscopy Infrared spectroscopy Anthraquinone Ionization Ligand Electrochemistry Density functional theory Mass spectrometry
Content Type	Text
Resource Type	Article
Subject	Chemistry

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