Time-resolved IR spectroscopy of a trinuclear palladium complex in solution.

This paper presents a combined spectroscopic and theoretical analysis of a trinuclear [Pd3{Si(mt(Me))3}2] complex (mt(Me) = methimazole) which has been demonstrated to be a potential catalyst for coupling reactions. It is a highly symmetric model system (D3 in the electronic ground state) for the investigation of electronic states and the structure of polynuclear transition metal complexes. Different time-resolved IR spectroscopic methods covering the femtosecond up to the microsecond range as well as density functional computations are performed to unravel the structure and character of this complex in the electronically excited state. These are the first time-resolved IR studies on a trinuclear Pd complex. Based on the interplay between the computational results and those from the IR studies a (3)A state is identified as the lowest lying triplet state which has C2 symmetry.

[1]  Manoj K. Kesharwani,et al.  Frequency and zero-point vibrational energy scale factors for double-hybrid density functionals (and other selected methods): can anharmonic force fields be avoided? , 2015, The journal of physical chemistry. A.

[2]  M. Nielsen,et al.  Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses , 2015, Nature Communications.

[3]  Tadesse A. Assefa,et al.  Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy)2]2+ , 2015, The journal of physical chemistry. C, Nanomaterials and interfaces.

[4]  K. Ohkubo,et al.  Electronic infrared light absorption of a tri-palladium complex containing two π-expanded tetracene ligands , 2014 .

[5]  W. Thiel,et al.  Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution , 2014 .

[6]  W. Klopper,et al.  In-depth exploration of the photophysics of a trinuclear palladium complex. , 2014, Physical chemistry chemical physics : PCCP.

[7]  V. Sundström,et al.  Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X-ray Absorption Spectroscopy , 2014 .

[8]  Montserrat Gómez,et al.  Polymetallic complexes linked to a single-frame ligand: cooperative effects in catalysis. , 2013, Dalton transactions.

[9]  T. Brixner,et al.  Ultrafast Photochemistry of a Manganese-Tricarbonyl CO-Releasing Molecule (CORM) in Aqueous Solution. , 2013, The journal of physical chemistry letters.

[10]  R. Crabtree,et al.  Redox-active ligands in catalysis. , 2013, Chemical Society reviews.

[11]  I. Bersuker.  Pseudo-Jahn-teller effect--a two-state paradigm in formation, deformation, and transformation of molecular systems and solids. , 2013, Chemical reviews.

[12]  Sukwon Hong,et al.  Cooperative bimetallic catalysis in asymmetric transformations. , 2012, Chemical Society reviews.

[13]  T. Ritter,et al.  Bimetallic redox synergy in oxidative palladium catalysis. , 2012, Accounts of chemical research.

[14]  Mónica H. Pérez‐Temprano,et al.  Bimetallic catalysis using transition and Group 11 metals: an emerging tool for C-C coupling and other reactions. , 2012, Chemistry.

[15]  Tourón Touceda Patricia,et al.  Transient infrared spectroscopy: a new approach to investigate valence tautomerism. , 2012 .

[16]  Christoph Van Wüllen,et al.  Shared-memory parallelization of the TURBOMOLE programs AOFORCE, ESCF, and EGRAD: How to quickly parallelize legacy code , 2011, J. Comput. Chem..

[17]  J. McCusker,et al.  Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics. , 2011, Journal of Physical Chemistry Letters.

[18]  P. Ford,et al.  Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices , 2011 .

[19]  J. Meyer,et al.  A triangulo palladium cluster consisting of μ3-capping silyl ligands. , 2011, Chemical communications.

[20]  Arjan W. Kleij,et al.  Cooperative multimetallic catalysis using metallosalens. , 2010, Chemical communications.

[21]  Jürgen Popp,et al.  Photophysics of an intramolecular hydrogen-evolving Ru-Pd photocatalyst. , 2009, Chemistry.

[22]  S. Johnson,et al.  Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex , 2009, Science.

[23]  R. Mathies,et al.  Femtosecond time-resolved optical and Raman spectroscopy of photoinduced spin crossover: temporal resolution of low-to-high spin optical switching. , 2008, Journal of the American Chemical Society.

[24]  J. McGarvey,et al.  Sub-picosecond time resolved infrared spectroscopy of high-spin state formation in Fe(ii) spin crossover complexes. , 2008, Physical chemistry chemical physics : PCCP.

[25]  M. Pettersson,et al.  Relaxation dynamics of Cr(acac)3 probed by ultrafast infrared spectroscopy. , 2007, Journal of the American Chemical Society.

[26]  M. W. George,et al.  Application of transient infrared and near infrared spectroscopy to transition metal complex excited states and intermediates , 2007 .

[27]  Jürgen Popp,et al.  Ultrafast excited-state excitation dynamics in a quasi-two-dimensional light-harvesting antenna based on ruthenium(II) and palladium(II) chromophores. , 2006, Chemistry.

[28]  D. Oesterhelt,et al.  Primary reaction dynamics of halorhodopsin, observed by sub-picosecond IR : vibrational spectroscopy , 2006 .

[29]  Jonathan A. Faiz,et al.  A Unidirectional Energy Transfer Cascade Process in a Ruthenium Junction Self-Assembled by α- and β-Cyclodextrins , 2006 .

[30]  M. Towrie,et al.  Ultrafast charge separation in a photoreactive rhenium-appended porphyrin assembly monitored by picosecond transient infrared spectroscopy. , 2006, Journal of the American Chemical Society.

[31]  R. Passalacqua,et al.  Dendrimers made of Ru(II) and Os(II) polypyridine subunits as artificial light-harvesting antennae , 2003 .

[32]  Filipp Furche,et al.  An efficient implementation of second analytical derivatives for density functional methods , 2002 .

[33]  J. Yeston,et al.  Direct Observation of a Picosecond Alkane C−H Bond Activation Reaction at Iridium , 2000 .

[34]  A. Vlček.  The life and times of excited states of organometallic and coordination compounds , 2000 .

[35]  P. Schollhammer,et al.  Dinuclear molybdenum thiolato-bridged compounds: syntheses, reactivities and electrochemical studies of site–substrate interactions , 1998 .

[36]  M. W. George,et al.  Excited states of transition metal complexes studied by time-resolved infrared spectroscopy , 1998 .

[37]  J. Treadway,et al.  Mid-infrared spectrum of [Ru(bpy)3]2+* , 1997 .

[38]  J. Treadway,et al.  Insights on the Excited State Electronic Structures of Ruthenium(II) Polypyridine Complexes Obtained by Step-Scan Fourier Transform Infrared Absorption Difference Time-Resolved Spectroscopy. , 1997, Inorganic chemistry.

[39]  R. Dyer,et al.  Time-Resolved, Step-Scan FTIR Spectroscopy of Excited States of Transition Metal Complexes , 1996 .

[40]  E. Heilweil,et al.  Ultrafast transient infrared absorption studies of M(CO)6 (M Cr, Mo or W) photoproducts in n-hexane solution , 1994 .

[41]  M. Poliakoff,et al.  Fast time-resolved FTIR detection of short-lived photochemical transient species in solution: a direct comparison with IR laser spectroscopy , 1985 .

[42]  A. Maverick,et al.  Solar Chemistry of Metal Complexes , 1981, Science.