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Title: Molecular and Electronic Structure of Cyclic Trinuclear Gold(I) Carbeniate Complexes: Insights for Structure/Luminescence/Conductivity Relationships

An experimental and computational study of correlations between solid-state structure and optical/electronic properties of cyclotrimeric gold(I) carbeniates, [Au-3(RN=COR')(3)] (R, R' = H, Me, Bu-n, or (c)Pe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au-3(MeN=(COBu)-Bu-n)(3)], [Au-3((BuN)-Bu-n=COMe)(3)], [Au-3((BuN)-Bu-n=(COBu)-Bu-n)(3)], and [Au-3((c)PeN=COMe)(3)] are presented. Changes in R and R' lead to distinctive variations in solid-state stacking, luminescence spectra, and conductive properties. Solid-state emission and excitation spectra for each complex display a remarkable dependence on the solid-state packing of the cyclotrimers. The electronic structure of [Au-3(RN=COR')(3)] was investigated via molecular and solid-state simulations. Calculations on [Au-3(HN=COH)(3)] models indicate that the infinitely extended chain of eclipsed structures with equidistant Au-Au intertrimer aurophilic bonding can have lower band gaps, smaller Stokes shifts, and reduced reorganization energies (lambda). The action of one cyclotrimer as a molecular nanowire is demonstrated via fabrication of an organic field effect transistor and shown to produce a p-type field effect. Hole transport for the same cyclotrimer-doped within a poly(9-vinylcarbazole) host-produced a colossal increase in current density from similar to 1 to similar to 1000 mA/cm(2). Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.
Authors:
 [1] ;  [1] ;  [2] ;  [2] ;  [3] ;  [4] ;  [1] ;  [1] ;  [2] ;  [1]
  1. University of North Texas
  2. University of Texas at Dallas
  3. Ibn Tofail Univ, ESCTM, Morocco
  4. ORNL
Publication Date:
OSTI Identifier:
1154878
DOE Contract Number:
DE-AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 53; Journal Issue: 14
Research Org:
Oak Ridge National Laboratory (ORNL)
Sponsoring Org:
SC USDOE - Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
TOTAL-ENERGY CALCULATIONS; FIELD-EFFECT TRANSISTORS; AU-AU INTERACTIONS; WAVE BASIS-SET; CRYSTAL-STRUCTURE; CHARGE-TRANSPORT; INTERMOLECULAR INTERACTIONS; SUPRAMOLECULAR STRUCTURE; AUROPHILIC INTERACTIONS; ORGANIC SEMICONDUCTORS