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Title: Organometallic Iridium Complex Containing a Dianionic, Tridentate, Mixed Organic–Inorganic Ligand

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388185
DOE Contract Number:
SC0001059
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 55; Journal Issue: 16; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), solar (photovoltaic), solar (fuels), photosynthesis (natural and artificial), bio-inspired, hydrogen and fuel cells, electrodes - solar, defects, charge transport, spin dynamics, membrane, materials and chemistry by design, optics, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Bloomfield, Aaron J., Matula, Adam J., Mercado, Brandon Q., Batista, Victor S., and Crabtree, Robert H. Organometallic Iridium Complex Containing a Dianionic, Tridentate, Mixed Organic–Inorganic Ligand. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.6b01218.
Bloomfield, Aaron J., Matula, Adam J., Mercado, Brandon Q., Batista, Victor S., & Crabtree, Robert H. Organometallic Iridium Complex Containing a Dianionic, Tridentate, Mixed Organic–Inorganic Ligand. United States. doi:10.1021/acs.inorgchem.6b01218.
Bloomfield, Aaron J., Matula, Adam J., Mercado, Brandon Q., Batista, Victor S., and Crabtree, Robert H. 2016. "Organometallic Iridium Complex Containing a Dianionic, Tridentate, Mixed Organic–Inorganic Ligand". United States. doi:10.1021/acs.inorgchem.6b01218.
@article{osti_1388185,
title = {Organometallic Iridium Complex Containing a Dianionic, Tridentate, Mixed Organic–Inorganic Ligand},
author = {Bloomfield, Aaron J. and Matula, Adam J. and Mercado, Brandon Q. and Batista, Victor S. and Crabtree, Robert H.},
abstractNote = {},
doi = {10.1021/acs.inorgchem.6b01218},
journal = {Inorganic Chemistry},
number = 16,
volume = 55,
place = {United States},
year = 2016,
month = 7
}
  • The stereoselective oxidative addition of H{sub 2} to IrCl(CO)(dppe) was examined with ab initio theoretical techniques. Reaction coordinates for the two pathways to addition which lead to the formation of the two isomers were constructed from geometry optimization calculations and were augmented by significant portions of the potential energy surfaces near the transition states. The analysis of the Laplacian of the total charge densities revealed that as the complexes evolve from four-coordinate to six-coordinate species, the ligands in the plane of addition move past regions of charge concentration around the metal center. Electron-withdrawing ligands in the plane of addition reducemore » this repulsive interaction by delocalizing a portion of the electronic charge. Electron-donor ligands are unable to function in this capacity and therefore contribute to the repulsive interaction of the five-coordinate transition state to a greater extent. The influence of electron correlation on the reaction coordinates was examined and found not to significantly after the conclusions based on the single-determinant calculations. 25 refs., 12 figs.« less
  • The title complex, [VO{sub 2}(C{sub 6}H{sub 5}C(O)CHC(CH{sub 3})NNC(O)CH{sub 2}(NC{sub 5}H{sub 5}))]{center_dot}C{sub 2}H{sub 5}OH, was synthesized and characterized by elemental analysis and spectroscopy. Yellow crystals of the complex are monoclinic, space group P2{sub 1}/a with a = 10.690(2), b = 16.008(3), c = 13.164(4){Angstrom}, {beta} = 107.03(2){degrees}, V = 2153.9(18){Angstrom}{sup 3}, F(000) = 880 and Dc = 1.305 g cm{sup -3} for Z =4. X-ray structure analysis shows that the vanadium coordination number is five and the coordination polyhedron is a distorted trigonal bipyramid.
  • The space group of P(N(C/sub 6/H/sub 5/)PF/sub 2/)/sub 3/ Mo(CO)/sub 3/ is P2/sub 1//c. The unit cell parameters are a = 8.683(1) A, b = 28.218(7) A, c = 15.338 (2) A, and ..beta.. = 118.12 (1)/sup 0/. The structure is that of an octahedral fac-L/sub 3/ Mo(CO)/sub 3/ complex. The ligand has its PF/sub 2/ groups linked to the Mo atom. (DLC)
  • Graphical abstract: Display Omitted Highlights: ► Novel organic–inorganic hybrid chlorobismuthate(III). ► Unprecedented dielectric response in non-polar material. ► Dielectric relaxation characterized by an exceptionally large dielectric increment. ► The NMR measurements confirmed dynamic disorder of cations. -- Abstract: The structure of [C{sub 2}H{sub 5}NH(CH{sub 3}){sub 2}{sup +}]{sub 3}[BiCl{sub 6}{sup −}] (abbreviated as DCB) was determined by a single-crystal X-ray diffraction at 115 K. The compound adopts tetragonal symmetry with the space group I4{sub 1}/acd; a = 23.35 Å, c = 17.60 Å, V = 9598 Å{sup 3} and Z = 16. The crystal structure of DCB is built up ofmore » isolated [BiCl{sub 6}]{sup 3−} units and N,N-dimethylethylammonium counterions that are accommodated in the large voids. At ambient temperature two-thirds of the counterions appear to be dynamically disordered. Dynamics of this type of cations contributes to the enhanced dielectric permittivity of DCB. A low frequency dielectric relaxation process that takes place between 200 and 300 K is characterized by an exceptionally large dielectric increment, Δε > 100, which is unprecedented in nonferroelectric materials. The molecular motions of the N,N-dimethylethylammonium cations were studied by means of {sup 1}H NMR spin-lattice relaxation time measurements.« less
  • In this paper, treatment of N-ethyl-benzo[f]quinolium (ebq) iodide and CuI with excess KI afforded an unusual coordination polymer [(ebq){sub 2}(Cu{sub 3}I{sub 4})(CuI{sub 2})]{sub n} (1). 1 crystallizes in tetragonal system, space group P4(2)bc with cell parameters of a=23.2040(6)A, c=6.7393(3)A, V=3628.6(2)A{sup 3}, Z=8, D{sub c}=2.622g/c{sup 3}, R{sub 1}=0.0447 and wR{sub 2}=0.0974. A highly interesting feature of 1 is its presence of mixed types of chains [(Cu{sub 3}I{sub 4}){sub n}{sup -} and (CuI{sub 2}){sub n}{sup -} chain] in one crystal lattice based on supramolecular self-assembly directed by cations. The infinite chains (Cu{sub 3}I{sub 4}){sub n}{sup -} and (CuI{sub 2}){sub n}{sup -} inmore » 1 could be described as the edge-sharing arrangement of CuI{sub 4} tetrahedron. Furthermore, IR, EA, UV-Vis, thermal analysis and optical limiting measurements were adopted to characterize polymer 1. The optical limiting experiment shows that the present polymer exhibits a large optical limiting capacity.« less